Strikers Alexandre Pato and Neymar scored two goals apiece as holders Brazil beat Ecuador 4-2 to finish top of Group B at the Copa America on Wednesday and set up a quarter-final against Paraguay.
The result left Venezuela with second place in the group and a last-eight meeting with Group C winners Chile in San Juan.
The other quarter-finals pit hosts Argentina against Uruguay and Colombia with Peru.
Ecuador bowed out of the tournament with two good goals from Felipe Caicedo in an exciting match that capped a lively final night for the South American tournament's group stage.
Venezuela earlier mounted a remarkable late comeback to snatch a 3-3 draw against Paraguay in Salta.