In 1944 Di Stéfano’s father wrote a letter of recommendation to River Plate, and the club sent a reply telegram to invite him to an audition with the youth team. Di Stéfano impressed on the trial and joined the second team squad of River Plate, the club his family supported. The next year he became part of the first team which was called La Máquina due to their unprecedented success, consisting of players like the legendary Pedernera, Labruna Muñoz, and Loustau. One of the main stars of the team, Moreno, had just left for the Mexican Real Club España and it seemed like a good opportunity for the young Di Stéfano to fight for a place on the first squad. Di Stéfano, whose idol was Paraguayan Arsenio Erico, the Independiente striker, learned from the big stars, especially Pedernera. His coach and first mentor Carlos Peucelle taught him how to play the ball low and soon he made his first team debut in 1945, at the age of 19: on 15 July of that year he debuted against Huracán in a 2–1 defeat on the twelfth day of the 1945 Argentine championship. This was the only game Di Stéfano played in that year, but at the end of the season he won his first title as River Plate won the championship, four points ahead of Boca Juniors.

Former Argentine striker and World Cup top scorer Guillermo Stábile, the Huracán and Argentine national team coach at the time, gave Di Stéfano his first real opportunities in the 1946 season. He scored the first two goals of his career in a 3–1 victory against Estudiantes (LP). He later scored against his former team River Plate, netting the fastest goal in the history of the Argentine championship after about ten seconds of play. He would score 10 goals in 25 appearances for Huracan, teaming up perfectly with Norberto Méndez who would later become the all-time top scorer in Copa América. Huracán tried to sign Di Stéfano permanently at the end of a successful eighth-place season, but could not afford the 90,000 pesos River Plate asked for the transfer.

The league victory gave River Plate the right to represent Argentina in the Copa Aldao against the champions of Uruguay Nacional Montevideo who featured great player like goalkeeper Anibal Paz and Walter Taibo in a two-nation club competition that tracked origins to 1913 and for many it was considered as the precursor to the Copa Libertadores. On November 1947, River beat Nacional 4–3 with Di Stéfano scoring one goal in Montevideo, and four days later Di Stéfano celebrated his first international club trophy with a 3–1 victory in Buenos Aires.

Di Stéfano made his international debut on 4 December 1947, in a match against Bolivia at the Estadio George Capwell in Ecuador, during the 1947 South American Championship. He scored his first international goal in that same match, helping Argentina to a 7–0 win. Di Stéfano scored five more goals during the championship – including his first hat-trick against Colombia – as Argentina successfully defended the title they had won the previous year on home soil.

In February 1948, champions River Plate participated in the inaugural South American Championship of Champions in Santiago facing the other South American champions, finishing second behind Vasco da Gama with Di Stéfano scoring 4 goals in 6 games. During the Argentinian championship of 1948, the Football Association suspended the tournament for a short time due to the protests of players led by Adolfo Pedernera and Alfredo Di Stéfano that resulted in a player’s strike in a bid to gain professional status and rights. Despite that upheaval Di Stéfano scored 13 goals in 23 games and River Plate finished third. The strike lasted for 8 months until 1949 and it eventually meant the departure of the best Argentine footballers to other leagues, in particular Colombia’s, which was one of the most lucrative in the world at the time. In one of his last games in Argentina, on 31 July 1949, Di Stéfano played in the role of goalkeeper, replacing the owner Amadeo Carrizo for twenty minutes and keeping the clean sheet in a derby won against Boca Juniors.

The Colombian league had turned professional in 1948, beginning the El Dorado period on 25 April 1949. Di Stéfano, Perdenera, and Nestor Rossi who joined Millonarios in the summer, formed the famous trio called the Ballet Azul and helped them win their first title ever beating Deportivo Cali in the 1949 final, with Di Stéfano scoring 16 goals in 14 games. Di Stéfano scored 23 goals in 29 games the following 1950 season, but Millonarios finished 2 points behind eventual champions Deportes Caldas. Di Stéfano, who kept himself in excellent condition, excelled during his games and led Millonarios to a second title in 1951, leaving runners-up Boca Juniors de Cali 11 points behind at the final table. Di Stéfano scored 32 goals in 34 games, more than any other player in the league. Millonarios would go on to lose the 1951 Copa Colombia (played in 1952) to Boca Juniors de Cali.

After the Superga air disaster, in May 1949, a friendly match between River Plate and Grande Torino was played and Di Stéfano was promised to the Granata. However the Argentine forward was soon after contacted by Adolfo Pedernera, who had already agreed to terms with the Colombian Bogota-based club Millonarios F.C.. On 9 August 1949, after another one of his teammates, Néstor Rossi signed for the Colombian club without River Plate receiving any compensation for the transfer as the Colombian FA was still not affiliated with FIFA, Di Stéfano signed with the Colombians. Millonarios, who could not afford to pay the transfer fees anyhow, offered him a salary clearly higher than that at River Plate, and the Argentine forward started a new chapter in his career in Colombia, in period called El Dorado. Many international stars like the Hungarians Béla Sárosi, László Szőke, Lithuanian Vytautas Kriščiūnas, the Argentines René Pontoni, Héctor Rial, English Charlie Mitten from Manchester United for 5.000 pounds a year, Neil Franklin from Stoke City, French-Hungarian Ferenc Nyers, Italian Luigi Di Franco, the Brazilian legend Heleno de Freitas, and others had joined the league after legendary Perdenera first signed.

After moving to Bogota in 1949, during a break in the Colombian League in 1951, friendly matches were organised under the name of combined XI of the Colombian league. Di Stéfano – without ever holding a Colombian passport – made four appearances for the Colombian XI team, which did not appear in the official records of FIFA.

Di Stéfano married Sara Freites in 1950; they had six children: Alfredo, Ignacio, Sofia, Silvana, Helena, and Nanette. Sara died in 2005.

In October 1951 the División Mayor del Fútbol Profesional Colombiano agreed to the Pacto de Lima with FIFA, with the requirement that foreign players would return to their countries after October 1954. Di Stéfano scored a total of 267 goals in 292 goals for Milionarios, and is considered as one of the best footballers the history of the Colombian League.

The 1952 league had the same outcome: Milionarios overtook Boca Juniors de Cali, won their third title, and Di Stéfano was once again top scorer with 19 goals. In October 1952, Di Stéfano also led Millonarios to the Copa Colombia final after beating Deportivo Cúcuta by 2–1. The final would be played in May 1953, after Di Stéfano had already gone to Argentina.

In March 1952, Real Madrid organized a friendly tournament in the Spanish capital at its newly constructed home ground; River Plate was invited to participate in Real Madrid’s 50th-anniversary tournament. The tournament was called Bodas de Oro, but once Real Madrid’s Santiago Bernabeu heard about the new powerhouse in South America, Real Madrid cancelled the invitation to River Plate and invited the Colombians as the South American representative. The Colombians participated in the tournament and won it, after drawing 2–2 with Swedish champions IFK Norrköping and overcoming Los Blancos, who were managed by Uruguayan legend Hector Scarone, by a 4–2 margin with a brace from Saeta Rubia in the presence of President Santiago Bernabéu, who arrived to the stadium to observe Adolfo Pedernera. Instead, Bernabéu asked Millonarios about Di Stéfano and a deal was struck between him and Millonarios owner Alfonso Senor Quevedo. Millonarios would start a global tour and spearheaded by Di Stéfano, they would beat Hungary and world champions Uruguay.

FIFA appointed Armando Muñoz Calero, former president of the Spanish Football Federation as mediator. Calero decided to let Di Stéfano play the 1953-1954 and 1955-1956 seasons in Madrid, and the 1954-1955 and 1956–1957 seasons in Barcelona. The agreement was approved by the Football Association and their respective clubs. Although the Catalans agreed, the decision created various discontent among the Blaugrana members and the president was forced to resign in September 1953.

A 27-year-old Di Stéfano arrived at Real Madrid on 22 September 1953, after seven months of inactivity, and made his debut with the white jersey in October 1953 in a clásico against champions Barcelona, won 5–0 with a Di Stéfano hat trick. Real Madrid was an average team and had not won the title in 20 years. In his first several months in Madrid, the Argentine champion did not adapt to European football, but imposed his own style, playing all around the field with speed and keeping the ball low on the ground. In his first season with Real Madrid, Di Stéfano became the top scorer of the 1953–54 La Liga with 27 goals in 28 appearances, contributing significantly to the title victory as the Blancos managed to win the Spanish championship after two decades.

Soon after Millonarios’ return to Colombia, the Barcelona directors visited Buenos Aires and agreed with River Plate, the last FIFA-affiliated team to have held Di Stéfano’s rights, for his transfer in 1954 for the equivalent of 150 million Italian lira (according to other sources 200,000 dollars). This started a battle between the two Spanish rivals for his rights. In Christmas 1952, Di Stéfano, still contracted with Millonarios, returned briefly to Buenos Aires, where he was even making plans to abandon football and start a business as the Argentine league was still not professional.

The following year, Real Madrid acquired Argentine Héctor Rial from the Nacional Montevideo, a signing recommended by Di Stéfano, for the attack of the Merengues. The club won another league title in 1955 leaving Barcelona again in the second place of the table. Di Stéfano scored 25 goals, finishing behind only Juan Arza (28) among the scorers of the Spanish league. On 26 June 1955, the Spanish club won their first ever Latin Cup, beating Raymond Kopa and Just Fontaine’s Stade de Reims in the final in Paris 2–0.

The second consecutive Spanish title allowed Real Madrid to be the first Spanish representative in the inaugural Champions Cup in the 1955-1956 season. Di Stéfano made his Champions Cup debut against Servette in a 2–0 away win. In the league he was again the top scorer with 24 goals, but despite that, Athletic Bilbao won the tournament ahead of Barça and Real. In the Champions Cup the team had their way eliminating the Swiss and later Partizan Belgrade, after a suffering a 3–0 defeat in Yugoslavia. With the guidance of Di Stéfano they had an easy 4–0 victory in Madrid in the first leg, in December 1956. Real Madrid flew to Belgrade and despite the snowstorm that had hit the city in the previous days, the president Bernabéu agreed for the match not to be postponed. Unlike the Spaniards, the Partizan players did not suffer on the terrain, taking the lead and dominating the game. A penalty was awarded to Real Madrid, but Héctor Rial slipped when kicking and missed it. In the final minutes with the Serbians up by 3–0, Di Stéfano helped in defending and Real qualified despite a clear defeat. The Blancos eliminated Milan in the semi-finals [64] and entered the final in Paris against Raymond Kopa and Just Fontaine’s Stade de Reims. Real Madrid suffered in the first half, but Di Stéfano carried his teammates in a comeback to win the trophy 4–3. At the end of the year, on 18 December 1956, the first Ballon d’Or was awarded, and Di Stéfano missed on winning it by just 3 votes to Stanley Matthews.

In the summer of 1956, Real Madrid signed Raymond Kopa from the Stade de Reims. The French forward could not feature in the games due to the limit of foreigners in La Liga and had to wait for the Spanish naturalisation of Di Stèfano, who became a Spanish citizen in October 1956.

The season started early with the participation of Real Madrid in the 1956 Small Club World Cup in Caracas, Venezuela as European champions. The Spaniards faced Vasco da Gama, AS Roma and FC Porto playing against players like World Cup winnerAlcides Ghiggia and Vavá. Real won the trophy with 3 wins and Di Stéfano finished as top scorer of the tournament with 4 goals (same as Vavá).

Di Stéfano was widely loved in Spain, and having been banned from playing for Argentina, it made sense for Di Stéfano to play for Spain. FIFA initially refused to sanction this, but after Di Stéfano acquired Spanish citizenship in 1956, and amid pressure from the Spanish FA, the decision was eventually reversed. Di Stéfano consequently made his debut for Spain on 30 January 1957 in a friendly in Madrid, scoring a hat-trick in a 5–1 win to become one of a number of players born outside Spain to have appeared for their national team.

The season finished with the loss of the 1958 Generalísimo Cup after they lost 2-0 to Athletic Bilbao. As a result, Ferenc Puskás signed with Real Madrid in the summer of 1958 to strengthen the squad and Real Madrid would be blessed with one of the most lethal attacking pairs in the history of football. Nevertheless, Real finished second in the 1959 season behind Barça, with Di Stéfano finishing as the best scorer in the league for the fifth and last time, and the fourth in a row, with 23 goals.

On 16 July 1959, Real Madrid hosted a match against Pelé and his Brazilian club, Santos FC, during their European tour. It was one of the most anticipated games of the tour, given the reputation that Pelé had started building. Di Stéfano’s team would beat the Brazilians by 5–3. In December, France Football awarded Di Stéfano the 1959 Ballon d’Or, which he won ahead of teammate Raymond Kopa (who had already returned to Stade de Reims in the summer of 1959) and Juventus’s Welsh star John Charles. Puskás and Gento both finished in the top ten.

During the 1959–1960 season, the Madrilenos signed the Brazilian midfielder Didi who was a World Cup winner, former teammate of Garrincha and Pelé and the best player of the 1958 FIFA World Cup. Given that the Brazilian’s style of play was similar to Di Stéfano’s, the Brazilian often clashed with the Argentine and there were rumours that he asked for his release from the club’s management in the summer of 1960. But with Didi in the squad, the Blancos won their fifth consecutive Champions Cup. After eliminating Barcelona in the semifinals, Real Madrid played in the final of the Hampden Park in Glasgow in front of 135,000 spectators against Eintracht Frankfurt. Di Stéfano and Puskás scored three and four goals respectively, in a game considered to be among the finest in the history of football. Di Stéfano scored 8 goals in the 1960 competition, finishing second in the scorers’ chart won by Puskás. In the 1960 season, Real finished equal with Barcelona on the table, but the Catalonians were the ones to be awarded the title. Di Stéfano did not win the Pichichi award as Puskás was the topscorer of the league with 25 goals. Real Madrid lost the Generalísimo Cup to Atletico Madrid by 3–1 at home on 26 June 1960.

The new season started with the inaugural Intercontinental Cup and the 0–0 draw in the first leg of the final against Peñarol in Montevideo on 4 July. But in the second leg, Real beat the Uruguayans by 5–0 with Di Stéfano scoring one goal on 4 September 1960. On 13 December 1960, Di Stéfano came fourth on the 1960 Ballon d’Or voting, and for the first time, Real were knocked out of the 1960-61 Champions Cup, 4-3 against Barcelona after a controversial return match. Real easily won the 1961 title by a great margin to runners-up Atletico Madrid, but lost the final of the Generalísimo Cup again to Rojiblancos 3-2. Di Stéfano finished the season with 21 goals, second-highest scorer in the league behind Puskás who netted 28 goals.

In the 1961-1962 season Di Stéfano won the double for the first time, winning the Generalísimo Cup 15 years since the last time after beating Sevilla 2–1 with two goals from Puskás to overturn the initial red and white advantage. He finished 6th in the 1961 Ballon d’Or in December. In the 1961-62 European season, Real reached the final of the tournament for the sixth time in its history, after eliminating Juventus and Standard Liege. Real played against Eusébio’s Benfica and though the Spaniards took the lead twice, in the second half of the game the Lusitanians won the title 5–3, courtesy of Eusebio. Real lost its first European Cup final and for the first time Di Stéfano did not score in a final (the three goals were scored by Puskás). Nevertheless, he was among the best scorers of the competition for the second time in his career, with 7 goals.

In 1961, at the age of 36, Di Stéfano finally qualified for a World Cup, helping Spain qualify for the 1962 edition in Chile. A muscular injury just before the competition prevented him from playing in the finals, but Di Stéfano travelled with the squad anyway, picking the number 6 jersey as his preferred number 9 was taken by Francisco Gento. Spain boasted the likes of José Santamaría and Ferenc Puskás – both also naturalised citizens – but with Di Stéfano sidelined, they failed to make it out of the group stage, losing to Pelé and Didi’s Brazil in their final game and finishing at the bottom of their group. Di Stéfano retired from international football after the tournament.

The 1963-1964 season was the last for Di Stéfano at Real Madrid. At the beginning of the season, the team had a pre-season tour in Venezuela as the team participated in the 1963 Small Club World Cup against São Paulo and FC Porto. Di Stéfano played on the first match on 20 August, but on 24 August the Argentine champion was kidnapped by the National Liberation Armed Forces of Venezuela in the Potomac hotel in Caracas, and was released by them three days later, unharmed. The incident cost the Los Blancos the trophy as without Di Stéfano they could not overcome São Paulo in the final game.

On the night of 24 August 1963, the Venezuelan revolutionary group Armed Forces of National Liberation (FALN), kidnapped Alfredo Di Stéfano at gunpoint from the Potomac Hotel in Caracas while his team, Real Madrid, were on a pre-season tour of South America. The kidnapping was codenamed “Julián Grimau”, after the Spanish communist Julián Grimau García, executed by firing squad in Spain in April 1963 during Francisco Franco’s dictatorship. Di Stéfano was released unharmed two days later close to the Spanish embassy without a ransom being paid, and Di Stéfano stressed that his kidnappers had not mistreated him. Di Stéfano played in a match against São Paulo the day after he was released and received a standing ovation.

After the Champions Cup final loss in 1964 against Inter Milan, president Santiago Bernabéu offered Di Stéfano a place on the Real Madrid coaching staff instead of renewing the player’s contract. Di Stéfano refused Bernabéu’s proposal and he moved to Real Espanyol.

As Real Madrid did not win the title in the previous season, president Santiago Bernabéu, who also served as the vice-president of the competition, came up with the idea that the Champions Cup winner had the right to register for the next edition to defend the victory even if it had lost the championship. Consequently, Real participated in the 1956-1957 season, eliminating Rapid Vienna, Nice, and Manchester United in the semifinals and beating Fiorentina 2–0 in the final, in Madrid. During the season, Real also asserted itself in the last edition of the Latin Cup, overcoming Benfica 1–0 in the final with a decisive goal by Di Stéfano and at the end of the year, he won the 1957 Ballon d’Or. From the twenty-third day of the 1956-1957 championship, Real Madrid started a series of consecutive victorious home results that ended only in 1966, at the twenty-fifth round of the Liga, after 121 matches. The Blancos attack was one of the best in history and boasted Di Stéfano, Héctor Rial, Francisco Gento and Kopa. Real won the 1957 championship and Di Stéfano was again the top scorer in the Liga with 31 goals.

The Argentine veteran scored 9 goals in all competitions in his first season with Espanyol, putting an end to a streak of 15 consecutive seasons in which he scored in double figures (18 total). After 14 goals in 60 matches with Espanyol, he retired as a player at 40 in 1966, helping his team avoid relegation in both seasons. Despite what was previously stated, Bernabéu decided to throw a farewell match against Celtic in Madrid, to honour him for his services.

After retirement, Di Stéfano moved into coaching. He guided the Argentine club Boca Juniors to a league title, and won La Liga and the European Cup Winners’ Cup with Valencia. He also returned to Valencia in 1986 to guide them back to La Liga by winning the Segunda Division after their relegation the season prior before his arrival. He also managed Sporting in the 1974–75 season and Real Madrid between 1982 and 1984. In the 1982–83 season they finished third in La Liga and were defeated in the finals of the Supercopa de España, Copa de la Liga, and Copa del Rey. Madrid were also beaten by Aberdeen, managed by Alex Ferguson, in the European Cup Winners’ Cup final.

A Spanish movie entitled Real, La Película (Real, The Movie), which recounted these events, was released on 25 August 2005. In a bizarre publicity stunt at the premiere, kidnapper Paul del Rio, now a famous artist, and Di Stéfano were brought together for the first time since the abduction, 42 years before.

On 24 December 2005, 79-year-old Di Stéfano suffered a heart attack.

On 9 May 2006, the Alfredo Di Stéfano Stadium was inaugurated at the City of Real Madrid, where Real Madrid usually train. Its inaugural match was between Real Madrid and Stade de Reims, a rematch of the European Cup final won by Real Madrid in 1956. Real Madrid won 6–1 with goals from Sergio Ramos, Antonio Cassano (2), Roberto Soldado (2), and José Manuel Jurado.

In 2013, an 86-year-old Di Stéfano was in a relationship with his 36-year-old personal secretary, Gina González. He announced his plans to marry her in the same year, but died before this happened.

Di Stéfano resided in Spain until his death in 2014. On 5 November 2000 he was named Honorary President of Real Madrid.

Following another heart attack on 5 July 2014, the 88-year-old Di Stéfano was moved to intensive care in the Gregorio Marañón hospital in Madrid, where he died on 7 July 2014.

The Club Atlético River Plate from Argentina and Millonarios Fútbol Club from Colombia organized a friendly match in homage of their former player. The match was played on 16 July 2014, at the Millonarios’ Estadio El Campín.