Alves spent his first four years in Spain with Almeria after joining from Atletico Mineiro, keeping out 12 of the 18 spot kicks he faced with the Andalusian outfit before switching to Valencia in 2011 for three million euros (2.63 million pounds).
He further cemented his reputation as a penalty-saving specialist by denying Lionel Messi from the spot in the first spot kick he faced as a Valencia player and last season saved two penalties during a defeat to Atletico Madrid, one from Antoine Griezmann and the other from Gabi.
Last September Alves, 32, made a record-breaking 17th penalty save in Spain's top flight in a 2-1 win at Leganes, taking him ahead of former Barcelona goalkeeper Andoni Zubizarreta.
He broke another record in April when he denied Cristiano Ronaldo from the spot to accumulate six penalties saved in a season, conceding only three spot kicks over the course of the campaign.
In total, he saved 24 of the 50 penalties he faced in La Liga, conceding 24, while two missed the target.
Valencia announced his departure in a brief statement on their official website, saying: "Valencia closed a deal with Flamengo on Sunday for the definitive transfer of the rights of goalkeeper Diego Alves to the Brazilian club."
According to reports in Spain, Flamengo have signed Alves on a four-year contract for less than 500,000 euros.
(Reporting by Richard Martin; Editing by Clare Fallon)
