Former Manchester City and Everton striker Jo - now playing club football for Copa Libertadores champions Atletico Mineiro - bagged a brace, while Neymar, Ramires, Alexandre Pato and Luiz Gustavo wrapped up a comfortable win for Luiz Felipe Scolari's side.
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It took six minutes for the Selecao to breach the Aussie defence, with Jo applying the finish after Bernard had struck the post with an excellent volley from Neymar's cross.
The 26-year-old striker then doubled the lead on 33 minutes, this time finishing a cross from the Shakhtar Donetsk winger, before Neymar made it 3-0 when he raced through to slot past Mark Schwarzer.
Ramires got his name on the scoresheet by powering in a header from Maxwell's cross in the 58th minute.
A superb through-ball from Neymar allowed Pato to add a fifth in the 71st minute, before Gustavo rattled home a sixth with a powerful 25-yard effort eight minutes from the end.