Head coach Tite has stripped the PSG winger of the captaincy, instead naming his team-mate as skipper for the summer tournament
Paris Saint-Germain superstar Neymar was named permanent Brazil captain by head coach Tite in September 2018, however, he has been replaced by 36-year-old club and country team-mate Alves.
In a statement released on Monday, the Brazilian Football Confederation (CBF) said: "The decision was communicated to Neymar by Tite on Saturday."
The announcement comes after a turbulent end to the season for Neymar at Ligue 1 champions PSG, where coach Thomas Tuchel has ruled out the former Barcelona star becoming captain.
Brazil are set to host the Copa America, with the eight-time champions – who failed to progress beyond the group stage in 2016 – drawn alongside Bolivia, Peru and Venezuela in Group A.
Tite's Brazil will open the tournament against Bolivia in Sao Paulo on June 14.