Born in La Pobla de Segur, Lleida, Catalonia, Puyol started playing football for his hometown club as a goalkeeper, but after injury problems with his shoulder he switched to forward. He said that in his youth, “My parents were skeptical about me becoming a footballer and encouraged me to study.” In 1995, he joined FC Barcelona’s youth system at La Masia, switching positions again, to play as a defensive midfielder; two years later, he started playing for the club’s B-team, occupying the position of right-back.

In 1998, Barcelona accepted an offer from Málaga CF to sell Puyol, who was behind Frank de Boer and Michael Reiziger in the pecking order. However, he refused to leave after seeing his best friend Xavi make his first-team debut.

Louis van Gaal promoted Puyol to the first team the following year, and he made his La Liga debut on 2 October 1999 in a 2–0 away win against Real Valladolid. After that he successfully made another conversion, to central defender. During the 2003 off-season, as Barcelona was immersed in a financial crisis, Manchester United showed interest in signing Puyol, but no move ever materialised. Two years later, he extended his contract for a further five seasons.

Puyol won his first cap for Spain on 15 November 2000 against the Netherlands, and remained a regular fixture in the following years. He played for his country at the 2000 Olympics, 2002 FIFA World Cup, UEFA Euro 2004, 2006 World Cup, Euro 2008, 2009 FIFA Confederations Cup and the 2010 World Cup.

Puyol was named club captain at the end of 2003–04, after the retirement of Luis Enrique. He continued to be a defensive cornerstone for Barça, being awarded the “Best European right-back” award by UEFA in 2002 (amongst other individual accolades), and helped the Catalans win two consecutive league titles. In 2005–06 he appeared in a total of 52 games, including 12 in that season’s UEFA Champions League which ended in victory against Arsenal, the club’s second European Cup.

During the 2002 World Cup, Puyol scored an own goal in the 3–1 win over Paraguay in the group stages. In the round of 16 tie against Ireland, he assisted Fernando Morientes; following a 1–1 deadlock after extra-time, his team prevailed following a 3–2 penalty shoot-out victory. Spain were eliminated in the quarter-finals of the competition by co-hosts South Korea, after a 5–3 shoot-out defeat.

Described as a “no–nonsense” player, Puyol was known for his commanding presence in the air despite his modest stature, as well as his ability to read the game, and his intense commitment and ruggedness as a defender, in particular when challenging for the ball. According to Barcelona’s head doctor, he was “the strongest, who has the quickest reactions, and who has the most explosive strength.” In 2006, Simon Talbot of The Guardian described Puyol as: “Barcelona’s very own Captain Caveman, playing football with his heart on his sleeve and his hair in his eyes, throwing himself about the pitch and launching wholeheartedly into kamikaze tackles like a hyperactive, lunatic kid.” Club fans referred to him as “The Wall”.

In 2006, Puyol said that when not working, he leads “a very quiet life… I’ve not been to a nightclub in Barcelona for years either. When I go out, I stay in a restaurant with my friends.”

Puyol’s father, Josep, died in a farming accident in late 2006 while Carles was on his way to play a match against Deportivo de La Coruña. He was informed of the news by coach Frank Rijkaard upon landing. He said that this, combined with an injury led to a dark period, with Spain national team physio Raúl Martínez eventually coming to Barcelona: in the player’s words, “…[he] gave me a great telling off. He made me react, and I began to try to be more cheerful, and not overwhelmed by it all.”

On 16 September 2008, Puyol made his 400th appearance for Barcelona in a Champions League group stage match against Sporting CP. In the league season, despite injury problems, he appeared in 28 matches and helped them win another league title. His only goal came against Real Madrid in El Clásico at the Santiago Bernabéu on 2 May 2009 which finished with a resounding 6–2 win, and he celebrated his goal by kissing his Catalan flag armband in front of the incensed Madrid fans. He was essential to the team also winning the 2009 Copa del Rey, the 2009 Champions League, the 2009 UEFA Super Cup and the 2009 FIFA Club World Cup to complete an unprecedented sextuple, appearing in nearly 100 official matches.

In March 2009, Puyol told Goal.com: “I do not like to go out much, although it is good to disconnect and I like to read.” In September 2010, he started a relationship with model Malena Costa. In October of that year, he scored through a header in a 2–1 home win against Valencia CF and dedicated the goal to her by making a heart symbol with both hands. “I dedicate the goal to my girlfriend”, he said after the game.

On 13 November 2010, Puyol played his 500th game in all competitions for Barcelona in a domestic league match against Villarreal CF. He struggled again with injuries during the 2010–11 campaign, but still appeared in 28 matches, again winning the league and the Champions League. He played six minutes in the Champions League final, a 3–1 victory over Manchester United.

In the 2010 World Cup in South Africa, Puyol started every match and played almost every minute (he was replaced by Marchena in the 84th minute of the quarter-final against Paraguay). He scored the only goal in the semi-final with Germany, a powerful header from a corner taken by Barcelona teammate Xavi, which sent the national team through to their first World Cup final. In the decisive match, he featured for the full 120 minutes as the side defeated the Netherlands 1–0. Spain only conceded two goal throughout the tournament – none of which came in the knock-out stages – also keeping five clean sheets, a record for a World Cup–winning team, shared with the 2006 Italy side and 1998’s France. He also completed 88% of his passes, the third–highest completion rate of any player in the competition alongside his teammate Sergio Busquets, and was named to the team of the tournament for his performances.

On 1 August 2010, aged 32, Puyol announced that he would continue to represent the national team for at least another two years. He missed Euro 2012 due to a knee injury sustained in a league game against RCD Espanyol in early May, which required surgery and five to six weeks’ recuperation. The following year, he was ruled out of the Confederations Cup, once again due to physical problems.

Puyol was also known for his leadership and work ethic. He often continued training alone after the end of a team practice session or on days off. He said in 2010, “I don’t have Romário’s technique, [Marc] Overmars’ pace or [Patrick] Kluivert’s strength. But I work harder than the others. I’m like the student who is not as clever, but revises for his exams and does OK in the end.” Although his positioning, leadership and ability to organise his defence were initially cited as weaknesses early on in his career, he worked to improve on these aspects of his game throughout his time with Barcelona. Indeed, Miguel Ángel Nadal, who played with him for a short period of time, later said, “Carles plays with maturity, has great positional sense, and above all, has pride in his shirt.” A physical yet fair player, he was also known for his anticipation, strength, aggression, determination, discipline, intelligence and concentration as a defender, as well as his man-marking skills and ability to organise his defence; he also excelled in one on one situations.

In 2011, Puyol paid €30,000 for specialist private treatment for Miki Roqué, a footballer from his home province who was suffering from pelvic cancer. Roqué died in 2012.

After the defeat to Inter Milan in the 2009–10 Champions League semi-final, Puyol played in 56 matches for Barcelona without losing, a run that only ended on 11 January 2012 at CA Osasuna (2–3 loss). He also scored two goals in the season’s Copa del Rey, against Real Madrid and Valencia CF.

On 2 October 2012, in the late stages of a Champions League group stage encounter at S.L. Benfica, his first game upon recovering from a knee ligament injury suffered against Getafe CF, Puyol dislocated his elbow after landing awkwardly in a corner kick challenge. He was initially expected to be sidelined for two months but fully recovered in one. On 18 December Barcelona renewed his contract, extending it until 30 June 2016. In June of the following year he again underwent surgery on his right knee, his sixth operation as a professional, which led to thoughts of early retirement.

Puyol started a relationship with Vanesa Lorenzo in 2012. The couple had two daughters, Manuela (born 2014) and María (2016).

Puyol played his 100th and final international on 6 February 2013, captaining Spain to a 3–1 friendly win over Uruguay in Doha, Qatar.

On 2 March 2014, Puyol surpassed Migueli to go second in Barça’s all-time league appearances table, behind only Xavi, and scored the third goal in a 4–1 home win against UD Almería. Two days later, although he still had two more years in his contract, he announced that he would leave Barcelona at the end of the season. He said “After my last two major operations, I find it is taking me a lot of effort to reach the level required here, even more than myself and the surgeons thought necessary. That’s the reason I have reached this decision”.

Barcelona bid farewell to Puyol on 15 May 2014, after a fifteen-year career in the first team (ten as captain) that brought him 21 titles. At a packed Auditori 1899, his teammates, ex-teammates, presidents and coaches paid tribute to him, and he said “I’ve lived the dream of so many young kids, doing what I most enjoy in life, playing football and training”. He announced his retirement shortly after at the age of 36 but stayed with his only club; he was immediately appointed director of football Andoni Zubizarreta’s assistant. He resigned in January 2015, shortly after Zubizarreta was fired.

Puyol was invited by Iranian television channel IRIB TV3 to provide commentary on the World Cup match between Iran and Spain on 20 June 2018 in a programme hosted by Adel Ferdosipour, but was not allowed in the studio. According to news website Entekhab, the former player said that he had been told by the Islamic Republic of Iran Broadcasting that he could not appear in the programme “because of his looks (long hair)”; the veteran channel director had been replaced by one closer to Iran’s ultra-religious hardliners weeks before, and this incident ultimately led to some ridicule within Iran on Twitter.

In September 2019, Puyol rejected an offer to become Barcelona’s sporting director.