Brazil's Olympics head coach Andre Jardine confirmed the squad on Thursday, with 38-year-old Sao Paulo full-back Alves one of three over-age players, along with Sevilla's Diego Carlos and Athletico PR goalkeeper Santos.
Former Barcelona, Juventus and Paris Saint-Germain star Alves, who has 118 international caps, was set to be part of Brazil's Copa America campaign but missed the showpiece CONMEBOL tournament due to a knee injury and will instead captain the Olympic side.
PSG star Neymar's absence is notable given he previously indicated he had wanted to be part of the Tokyo Games.
Aston Villa midfielder Douglas Luiz, Lyon's Bruno Guimaraes and Flamengo's Pedro have also been selected to represent Brazil.
Brazil won Olympic gold on home turf at the 2016 Games in Rio de Janeiro, with Neymar scoring the decisive penalty in a 5-4 shoot-out victory over Germany.
Jardine's side are grouped alongside Germany, Ivory Coast and Saudi Arabia in Group D for the Tokyo Olympics.
Brazil will face Germany in their opening game in Yokohama scheduled for July 22.
Brazil squad for Tokyo Olympics:
Santos (Athletico PR), Brenno (Gremio); Dani Alves (Sao Paulo), Gabriel Menino (Palmeiras), Guilherme Arana (Atletico Mineiro), Gabriel Magalhaes (Arsenal), Nino (Fluminense), Diego Carlos (Sevilla); Douglas Luiz (Aston Villa), Bruno Guimaraes (Lyon), Gerson (Flamengo), Claudinho (Red Bull Bragantino), Matheus Henrique (Gremio); Matheus Cunha (Hertha Berlin), Malcom (Zenit), Antony (Ajax), Paulinho (Bayer Leverkusen), Pedro (Flamengo).
The 2016 champions were pushed all the way by Jaime Lozano's side in Kashima but ultimately got the job done on penalties, successfully converting all four of their attempts to reach the final where they will face either Spain or Japan.
Guilherme Arana spurned the best chance of the first half in the 13th minute when he was denied by Guillermo Ochoa with just the goalkeeper in his way.
An even better opportunity looked set to fall Brazil's way soon after as Douglas Luiz was sent tumbling in the box, but the initial penalty award was overturned following a VAR review, with the Aston Villa midfield shown to have exaggerated contact with Jose Esquivel.
The second half was far tetchier, however, with opportunities a rare commodity at either end. The best Brazil could muster until the latter stages was a feeble Antony effort that caused Ochoa no concerns.
Ochoa was beaten in the 82nd minute but the post came to his rescue, with Richarlison's header coming off the inside of the upright but refusing to cross the line.
That saw the match go to extra time and rarely did either side look likely to make the breakthrough, with penalties long appearing a formality.
Eduardo Aguirre missed Mexico's first kick in the shoot-out after Dani Alves had converted, giving El Tri an uphill battle right from the start, and Johan Vasquez did no better with their second as he smashed against the post.
Charly Rodriguez at least got Mexico on the board, but Reinier followed the example set by Gabriel Martinelli and Bruno Guimaraes before him to slot home the decisive kick.
Brazil secured back-to-back golds on Saturday, following on from their Rio 2016 triumph with a 2-1 victory after extra time.
Mikel Oyarzabal levelled to bring Spain back into the game after Matheus Cunha's opener but Malcolm came off the bench to capture Olympic glory.
Alves, a three-time Champions League winner who also has six LaLiga titles on his resume, proclaimed Tokyo to be his greatest success in football.
"To be sincere, yes," the 38-year-old responded when asked if this was his greatest prize. "Because the others are every year, and I have competed time and time again, but with this medal, this is my last chance. I won’t make it to Paris.
"This means a lot for me. Everybody trusted in me, and I knew this would be a once-only opportunity, to be able to enjoy this dream. It’s not every day that you become an Olympic athlete, and even less at the age of 38.
"And so I came here like everybody else, as a virgin, to this competition. I came with the boys to live the dream with them. And we have managed it, after a lot of effort and sacrifice, and we are taking the biggest prize back home, back to our people."
Captain Alves and his team-mates were reduced to tears at the full-time whistle as Brazil came out on top in a record-breaking fifth final appearance.
The last trophy missing from his illustrious collection of honours is the World Cup, so could he keep on going for his country?
"I’m a dreamer, a small dreamer, and more than a dreamer, somebody who executes their dreams," he said in response to questions about Qatar 2022.
"The most important thing is to fight, and that’s what I know what to do. I have the drive of a 23-year-old.
"I still want to do big things in football, and have respect for the profession, because when you have respect for your profession, it brings you great things, and which is what I'm living."
