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

In December 2006, Alves 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 also played in every one of Sevilla's UEFA Cup matches which the club went on to win.

From his years in Spain he also acquired Spanish citizenship, thus allowing him to bypass any non-EU quota restrictions and exempting him from needing a work permit to play in any EU countries.

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

On August 16, 2007, Sevilla rejected an unspecified Chelsea bid and, six days later, rejected another two bids from Chelsea for Alves, considering them to be "way below what was expected". Alves later revealed his dismay with Sevilla 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, Alves set to stay at Seville after the death of team mate Antonio Puerta, with player and president appearing reconciled.

Barcelona
On July 2, 2008, Alves joined FC Barcelona. He left Sevilla in tears and said that he would love to join the club again.[citation needed] He said that he came to Sevilla as a boy and is now leaving as man.[citation needed] He broke down in tears at the press conference.[citation needed] The official price of the transfer stands at €29 million up front, with €6 million more to pay depending on a number of performance related factors over the next few seasons of Alves' Barcelona career, making Alves the world's most expensive right-back. Alves signed a four-year contract with Barcelona, that includes a buy-out clause of €90 million.