The Selecao ultimately topped Group B on goal difference as star duo Alexandre Pato and Neymar both netted a brace in the Cordoba showdown. Felipe Caceido also bagged a double for Ecuador, but it was not enough to lift the side from the bottom of the group standings.
Pato opened the scoring on 28 minutes when he headed in Andre Santos' cross. But Caceido had the teams heading into the half-time break on level terms after he made the most of a swift counter-attack to beat goalkeeper Julio Cesar.
Three minutes after the interval and Pato set up Santos starlet Neymar to restore Brazil's lead with a strike from inside the area, before Caceido equalised for a second time moments later.
But Brazil would make the most of their dominance as the second-half wore on, with Pato netting in the 61st minute and Neymar following that 10 minutes later to seal the win with another strike from close range.
Paraguay fought back from conceding an early goal, but managed to let in two goals in the final minutes to draw 3-3 with Venezuela in another six-goal thriller. The result sets up a fascinating quarter-final clash between Paraguay and Brazil.
The Paraguayans appeared to be cruising at 3-1 up in the second-half, but late goals from Miku and Grenddy Perozo ensured the points would be shared.
Salomon Rondon put Venezuela ahead after only four minutes when he fired a 20-yard shot past a helpless Justo Villar after dispossessing Nestor Ortigoza on the edge of the area. But Paraguay showed their class to claw their way back into the contest thanks to a scrappy Antolin Alcaraz strike from close range on 32 minutes following Lucas Barrios' looping header.
Barrios then put Paraguay ahead when he prodded in a parried strike from substitute Haedo Valdez, and when Cristian Riveros netted the team's third with just five minutes remaining, the victory appeared a formality for Gerardo Martino's men. However, Miku struck in the final minute of regular time to hand Venezuela a lifeline, setting the scene for Perozo to score the unlikeliest of equalisers in injury time, as goalkeeper Renny Vega helped the ball on from a corner for the defender to head home.
Venezuela will face heavyweights Chile in the quarter-finals after finishing second in the group to Brazil on goal difference.
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