After 2002–03, on loan to Sevilla from Bahia, Alves travelled to play in the 2003 FIFA World Youth Championship, where he impressed as Brazil won the tournament. He was named the third-best player of the tournament and, after this, the Sevilla move was made permanent.

In June 2006, Sevilla agreed to sell Alves to Liverpool, but Liverpool were unable to match Sevilla’s asking price of around £8 million. In December 2006, he signed a new contract with Sevilla, tying him to the club until 2012. He had a successful 2006–07 season, making 47 appearances and scoring 5 goals. He played in every one of Sevilla’s UEFA Cup matches, in a competition which the club went on to win.

Alves made his Brazil debut as a substitute in an unofficial friendly match against Kuwaiti club Al-Kuwait Selection on 7 October 2006. Three days later, he earned his first international cap in a friendly against Ecuador. He was included in Brazil’s team for the 2007 Copa América. He appeared in four matches including the final against Argentina on 15 July, where he gave an assist to Roberto Ayala’s own goal and scored a goal himself in the 3–0 victory.

On 1 August 2007, Alves told SporTV he wanted to leave Sevilla for a European giant, later reiterating his desire to leave Sevilla to Marca, saying he was flattered by Chelsea’s interest and that he could never turn down such an opportunity. In an interview with Antena 3 on 8 August, Alves confirmed his agent had been in England for some time handling Chelsea’s offer, urging Sevilla to at least consider the offer.

On 16 August 2007, Sevilla rejected an unspecified Chelsea bid and, six days later, rejected another two bids from Chelsea, considering them to be “way below what was expected”. Alves later revealed his dismay with Sevilla club president José María del Nido for having knocked back Chelsea’s offers for his services after his move to Stamford Bridge collapsed, with Chelsea signing fellow Brazilian full back Juliano Belletti for a much lower fee. After a public war of words between Alves and Del Nido, as well as the death of teammate Antonio Puerta, Alves decided to stay with Sevilla, with player and president ostensibly reconciled.

On 2 July 2008, Alves joined Barcelona, leaving Sevilla in tears and saying he would love to play for the club again. He said he came to Sevilla as a boy and was leaving as a man. The official price of the transfer stood at £23 million up-front, with approximately £7 million more depending on a number of performance-related factors over the next few seasons of Alves’ Barcelona career, making him one of the most expensive defenders in history and the third-most expensive player bought by Barça. He signed a four-year contract with Barcelona, which included a buy-out clause of €90 million. Alves made his competitive and European debuts for Barcelona against Wisła Kraków in the 2008–09 UEFA Champions League third-round qualifiers on 13 August 2008. He made his La Liga debut in the Liga season-opener away to Numancia on 31 August 2008. Later on in his debut season, he missed the 2009 UEFA Champions League Final due to a yellow-card suspension, although Barcelona nonetheless defeated Manchester United 2–0 to complete the treble after also winning La Liga and the 2008–09 Copa del Rey.

Despite being the most expensive right-back in history at the time, he was initially unable to hold down a regular starting spot in the Brazilian national team, with Maicon being the first choice ahead of him. Alves came on as a substitute in the 2009 FIFA Confederations Cup semi-final against South Africa and scored the winner, a free-kick and a goal in the 88th minute in a 1–0 win. The following summer, he was named to Brazil’s squad for the 2010 FIFA World Cup. He scored another long-range free-kick against Iran on 7 October 2010. The following year, Alves was included in Brazil’s 23-man squad for the 2011 Copa América in Argentina.

On 28 May 2011, Alves played in his first Champions League final as Barcelona defeated Manchester United 3–1 at Wembley Stadium to win its fourth European Cup.

On 29 September 2011, Alves was appointed as a Special Olympics Ambassador for its Global Football program, charged with promoting respect and inclusion in football for people with intellectual disabilities, particularly in the run up to the 2014 World Cup. Along with his ex-teammate turned rapper, José Manuel Pinto, Alves released a song called Suave on YouTube on 15 June 2018.

Alves was part of the 23 players called by coach Luiz Felipe Scolari to play in the 2013 FIFA Confederations Cup on home soil. He started in Brazil’s 3–0 victory over Spain in the final on 30 June, at the Maracanã Stadium.

On 27 April 2014, during a match at Villarreal’s stadium, El Madrigal, Alves was targeted by Villareal supporter David Campaya Lleo, who threw a banana at him. Alves picked up the banana, peeled it and took a bite. He responded to the incident by saying:

Teammate Neymar’s response – to post a photograph of himself on social media also eating a banana – went viral. Other footballers have also since taken photographs of themselves eating bananas. Cyrille Regis, who had been racially abused while a player in the 1970s and 1980s, expressed concern that the viral campaign would detract from the important issues of combating racism in the game. Alves said that whoever threw the banana at him should be publicly shamed, and on 30 April 2014, a man was arrested in connection with the incident. Villareal were later fined €12,000 for the incident.

On 7 May 2014, Alves was named to Brazil’s squad for the 2014 FIFA World Cup on home soil. He lost his position as a starter during the competition due to poor performances. After Brazil defeated Colombia 2–1 in the quarter-finals, Alves and teammate David Luiz were applauded for comforting James Rodríguez, an act they were both commended for by both Rodríguez and the media for showing respect.

On 6 June 2015, Alves started for Barça in the 2015 Champions League final as the club won its fifth European Cup by beating Juventus at the Olympiastadion in Berlin. This made Barcelona the first club in history to win the treble of domestic league, domestic cup and European Cup twice. Alves, Lionel Messi, Andrés Iniesta, Xavi, Gerard Piqué, Pedro and Sergio Busquets are the only players to have been a part of both treble-winning teams.

On 9 June 2015, Alves signed a two-year contract with Barcelona, keeping him at the club until 30 June 2017, with the option to extend a further year.

On 2 June 2016, Roberto Fernández, Barcelona’s technical secretary, announced Alves was leaving Barcelona that summer after eight years. Although under contract until 30 June 2017, Alves contract had a clause allowing him to leave as a free agent.

On 27 June 2016, Juventus announced the signing of Alves on a two-year deal with the option of a third year. He made his Juventus debut on 20 August in a 2–1 home win over Fiorentina in Serie A. On 21 September, Alves scored his first goal with Juventus in a 4–0 home win over Cagliari, before opening his Champions League account with the club against Dinamo Zagreb six days later. On 27 November, he suffered a broken leg in Juventus’ 3–1 defeat to Genoa. Alves made his return from injury as a substitute in a 1–0 Derby d’Italia win over Internazionale on 5 February 2017.

On 9 May 2017, Alves scored once and assisted a goal for Mario Mandžukić as Juventus defeated Monaco 2–1 to qualify for the 2017 Champions League final. Six days earlier, Alves had assisted both goals for Gonzalo Higuaín in the first leg of the tie at the Stade Louis II. On 17 May, Alves scored the opening goal of a 2–0 win over Lazio in the 2017 Coppa Italia Final. On 3 June, Alves appeared in his third UEFA Champions League final as Juventus were defeated 4–1 by Real Madrid at the Millennium Stadium in Cardiff.

On 29 June 2017, Alves had his contract with Juventus terminated by mutual consent. He made 33 appearances, winning the 2016–17 Serie A title and 2016–17 Coppa Italia in his one season in Turin.

On 12 July 2017, Alves joined French side Paris Saint-Germain on a free transfer, signing a two-year contract. He made his debut for the club on 29 July in the 2017 Trophée des Champions, scoring once and assisting the winning goal for Adrien Rabiot in a 2–1 victory over 2016–17 Ligue 1 champions Monaco. On 5 August, Alves assisted Edinson Cavani for PSG’s first goal of the 2017–18 Ligue 1 season in a 2–0 win over Amiens at the Parc des Princes.

On 8 May 2018, he started in the 2018 Coupe de France Final, as PSG defeated Les Herbiers VF 2–0 to clinch the 2017–18 Coupe de France title; he came off in the 86th minute for Thomas Meunier, after sustaining an injury.

On 28 August 2018, Alves announced through a post on his Instagram page changing his squad number from 32 to 13 in tribute to Brazilian legend and four-time World Cup winner Mário Zagallo.

Alves was picked as a starter in both the 2015 and Centenario Copa América tournaments by manager Dunga. He retained his position following the appointment of Tite and helped Brazil secure qualification for the 2018 FIFA World Cup, but was ruled out of the tournament due to a knee injury suffered in the 2018 Coupe de France Final.

After his contract with the club expired on 30 June 2019, Alves became a free agent.

On 1 August 2019, São Paulo FC announced the signing of Dani Alves on a contract that runs until December 2022. A lifelong supporter of São Paulo, Alves had previously on numerous occasions declared his wish of playing for the club. He received the number 10 shirt upon his arrival, and was subsequently deployed as an attacking midfielder. He made his debut on 18 August 2019, scoring the sole goal in a 1–0 league win over Ceará at the Morumbi.

In May 2019, he was included in Brazil’s 23-man squad for the 2019 Copa América on home soil. He went on to replace Neymar as Brazil captain for the tournament. In the team’s final group match against Peru in São Paulo on 22 June, Alves scored in a 5–0 win, which saw Brazil advance to the quarter-finals. In the final, on 7 July, at the Maracanã Stadium, Brazil faced Peru once again, and won the match 3–1 to win the title; Alves was subsequently named the Most Valuable Player of the tournament. The 2019 edition of the Copa América was the 40th title of his career.