The Socceroos were dealt a tough draw in Bahia on Friday when grouped with the two major European nations and Chile.
Spain beat Netherlands in the 2010 final and Chile finished as the third ranked team in South American qualifying, making Australia's task of progressing from Group B extremely difficult.
But Postecoglou is confident that his side will relish the challenge to make history in Brazil next year.
"(It's) obviously exciting. You're at a World Cup and we certainly wanted to play some of the big guns and we've got them all in our group which is fantastic," Postecoglou said.
"It'll be a great experience for us all and a chance for us to create some history for ourselves as a nation.
"(It's an) enormous challenge and a difficult group but as I said, that's what the World Cup is all about and we're all looking forward to it."
When asked if drawing Spain and Netherlands pleased him, Postecoglou responded: "Yeah. That’s what I mean. (And) Chile are a fantastic side, probably could have been seeded, should have been seeded.
"We're up against the best and for us as a nation, it's a great opportunity."
Postecoglou has only taken charge of one Australia match – a 1-0 friendly win over Costa Rica last month – after replacing Holger Osieck in October.
He won plaudits for his side's exciting style of football when with Australian clubs Brisbane Roar and Melbourne Victory, and the 48-year-old says his philosophy will not change despite the calibre of their opponents.
"There'll be some great football played in our group, that's for sure," he added.
"We'll play our part and I've got no doubt that when the competition is on, we'll give a great account of ourselves."
