The victory completed the quarter-final line up that will see hosts Chile face Uruguay on Wednesday, Peru take on Bolivia on Thursday, and Colombia line up against Argentina on Friday.
Saturday's tie between Brazil and Paraguay will be a repeat of four years ago when the Paraguayans advanced on penalties.
"Paraguay is a hard opponent, anyone who watched the last Copa America could see that they got to the final and deservedly so," defender Thiago Silva said on Brazilian television after the game.
Venezuela had never beaten Brazil in six Copa America games and their job was made all the harder after just nine minutes.
Thiago Silva, recalled to the side for this match after being dropped, opened the scoring in spectacular style when he volleyed home a corner from former Real Madrid striker Robinho.
Firmino doubled their lead six minutes into the second half when he leapt to volley home a cross from Willian on the left.
Nicolas Fedor got a consolation goal for Venezuela six minutes from time when he stooped to head home from close range after Jefferson had touched a free kick from Juan Arango onto the post.
The result takes Brazil's goalscoring record against Venezuela in the Copa America to 27 goals for to two against.
(Writing by Andrew Downie, editing by Nick Mulvenney)
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