The Manchester United boss is confident Australia can be the surprise packet of Group C and qualify for the Round of 16.
In a video for ESPN UK, Mourinho - renowned as one of the most successful managers of the current generation - predicted how each of the Groups at the World Cup would finish and he was positive Bert van Marwijk's side was capable of a historic run.
France was the two-time UEFA Champions League winner's pick to top Group C. However, second place would come down to a “big fight” between Australia, Denmark and Peru, with the Socceroos to come out on top and set up a clash against Lionel Messi's Argentina.
“I think France, no problems, will finish first,” Mourinho said.
“Big fight to finish second. I'll go for a surprise. C'mon Australia, let’s finish second!”
The Socceroos' run to the knockout stage wasn't the only bold World Cup prediction from the former Porto, Chelsea, Inter Milan and Real Madrid boss.
Mourinho tipped Russia to fight their way out of Group A in second place behind winners Uruguay.
"I think Russia has to finish second and the crucial match will be Russia against Egypt," he said.
The Portuguese manager was confident Cristiano Ronaldo and his team would be able to reach the knockout round but only after finishing second in their group behind Spain.
Mourinho also tipped Nigeria to surprise at the World Cup and finish ahead of Croatia and Iceland to snatch second place in Group D with Argentina to finish on top.
