Brazil last won the continental tournament in 2007, but as hosts of this year's edition are among the favourites to lift the trophy, alongside Argentina and Uruguay.
Reds pair Firmino and Alisson joined up with the rest of Tite's squad last week and both featured in the Selecao's final warm-up match ahead of Friday's Copa America curtain-raiser against Bolivia.
Returning to the fold following their Champions League exertions with Liverpool, Alisson was immediately restored as Brazil's No.1 and Firmino scored from the bench to help his nation thrash Honduras 7-0 in Porto Alegre on Sunday.