Teammate Dani Alves, the country 's football federation (CBF) has said.
The Copa America will be played on 14 June to 7 July, with hosts Brazil, who has not won the title since 2007, taking on Bolivia in the opening match in Sao Paulo before facing Venezuela and Peru.
"Daniel Alves will be captain of the Brazilian national team in the friendly matches against Qatar and Honduras and in Copa America Brazil 2019," the CBF said in a statement.
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Right-back Alves, who has 138 caps for Brazil, was made aware of his new role on Sunday.
The 36-year-old has captained his country on previous occasions, the last of which was a 1-0 friendly victory over Germany in 2018.
Brazil coach Tite had named Neymar standing captain a few months after Brazil's World Cup quarter-final exit at the hands of Belgium last year, 27-year-old due to his disciplinary issues.
PSG's French Cup final loss to Stade Rennes, and was also reportedly involved in a dressing room with PSG teammates.
Tite informed him on Saturday that he would not captain Brazil at the Copa America, the CBF said.