Globo Esporte report the 31-year-old was handed the armband by coach Ramon Menezes, who has temporarily filled the managerial void left by Tite.
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Regular captain Thiago Silva is absent after picking up an injury in Chelsea's 2-0 defeat at Tottenham last month.
Casemiro has skippered his country on a handful of occasions in the past but has never taken on the responsibility through a major tournament.
The report claims Casemiro is viewed as a 'leader' and a 'reference' for the crop of young stars arriving at the national team camp.
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He is among just ten players who represented Brazil at the World Cup, to be called up to Menezes squad.
Menezes is Brazil's U20 coach and has unsurprisingly opted for a young crop at senior level.
Chelsea's on-loan midfielder Andrey Santos is among the player's called up as is Tottenham defender Emerson Royal and Wolves midfielder Joao Gomes.
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Arsenal pair Gabriel Magalhaes and Gabriel Martinelli have missed out on the squad, while Liverpool goalkeeper Alisson and Newcastle's Bruno Guimaraes were also omitted.
Manchester United's Fred and Liverpool midfielder Fabinho were also left out as is Neymar who is recovering from ankle surgery.
Brazil have not played since their heartbreaking penalty shootout defeat to Croatia in the World Cup Quarter-final.
A stunning solo effort from Neymar put the tournament favourites ahead in extra time but they were pegged back three-minutes from time, forcing the shootout.
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Misses from Rodrygo and Marquinhos ultimately sealed Brazil's fate as they crashed out 4-2 on penalties.