Australia landed in Group B alongside reigning world champions and world No.1 side Spain, 2010 World Cup grand finalists The Netherlands and difficult South American team Chile, when the draw unfolded early Saturday morning (AEDT).
Far from being intimidated, Postecoglou is revelling in Australia's underdog status and says his charges will be out to shock the footballing world powers.
"It's not about being positive or putting on a brave face. This is what we want," he said after the draw was announced in Costa do Sauipe, Brazil.
"It's an enormous challenge for us but for a nation like ours that's exactly what we want.
"Hopefully once the World Cup comes round all the attention will be on the other three nations and we can go about our business quietly and efficiently.
"We've got a chance to make some headlines when the World Cup comes around."
The Socceroos will open their campaign against Chile on June 13, before playing The Netherlands on June 18 and Spain on June 23.
They may have avoided a clash with five-time world champions Brazil at home, but challenges don't get much bigger than taking on Spain, who shape as the biggest hurdle for the Socceroos of all three opponents.
It will be the first time Australia meet Spain, who have dominated world football in recent years winning the past two editions of the European Championship.
Vicente Del Bosque's men may have lost 3-0 to Brazil in July's Confederations Cup final but, with the likes of Sergio Ramos, Andres Iniesta, Fernando Torres and Sergio Busquets in their star-studded line-up, they are among the favourites at the 2014 World Cup.
The Dutch meanwhile have never beaten Australia in three previous encounters.
But that statistic will count for nothing come June with the ever-dangerous Dutch having stormed through qualifying, dropping only two points and scoring 34 goals courtesy of names like Manchester United star Robin van Persie.
Chile will also provide a stern test, having surged to a place in Brazil with a run of five wins and a draw in their six final qualifying matches.
They're the lowest-ranked of Australia's opponents but at world No.15, they're still well above the 59th-ranked Socceroos who are the lowest-ranked side in the 32-team tournament.
But while Postecoglou knows no-one is excepting Australia to do well, he's not shying away from the challenge.
"Everyone will be writing us off in this group, which is I think is logical," he said.
"But there's nothing like a challenge like that to bring the best out of an Australian team.
"From our perspective we've got some great opportunities to show the world we can play some good football against the best nations in the world."
In perhaps the only positive for Australia, they have avoided playing in the hot or humid parts of Brazil.
The Socceroos will be playing two matches in the cooler south of the country in Curitba against Spain and in Porto Alegre - the furthest south of all the 12 host cities - against The Netherlands.
The other group match against Chile in Cuiaba is in central Brazil.
The Socceroos have earmarked the small coastal town Vitoria, some 500km north of Rio de Janeiro, as their base for the month-long tournament.
Postecoglou said while there are still discussions to be had it was almost certain Vitoria would remain the Socceroos preferred base.
THE SOCCEROOS' SCHEDULE IN THE GROUP STAGE OF THE 2014 WORLD CUP IN BRAZIL:
Chile v Australia
Arena Pantanal in Cuiaba
1800 local time (0800 June 14 AEST)
Australia v Netherlands
Estadio Beira-Rio in Porto Alegre
1300 local time (0200 June 19 AEST)
Australia v Spain
Arena da Baixada in Curitiba
1300 local time (0340 June 24 AEST)
AUSTRALIA HEAD TO HEAD WITH GROUP B RIVALS:
v SPAIN: never played.
V NETHERLANDS: Played 3, Won 1, Drawn 2, Lost 0
- 04/06/06 Netherlands 1 drew Australia 1, Rotterdam (friendly)
- 06/09/08 Australia 2 def Netherlands 1, Eindhoven (friendly)
- 10/10/09 Australia 0 drew Netherlands 0, Sydney (friendly)
v CHILE: Played 4, Won 0, Drawn 1, Lost 3
- 22/06/74 Australia 0 drew Chile 0, Berlin (World Cup)
- 24/04/96 Chile 3 def Australia 0, Antofagasta (friendly)
- 07/02/98 Chile 1 def Australia 0, Melbourne (Optus World Series)
- 09/02/00 Chile 2 def Australia 0, Valparaiso (Four Nation Tournament)
GROUP B TEAM STATS:
World Cup appearances: 3 (1974, 2006, 2010)
Best finish: second round Germany 2006
World ranking: 59
Key players: Tim Cahill (New York Red Bulls), Robbie Kruse (Bayer Leverkusen), Mark Bresciano (Al-Gharafa), Tom Rogic (Celtic)
Coach: Ange Postecoglou (Aus)
First round: bye
Second round: bye
Third round: Group D winners. Oman 3-0 home 0-1 away, Thailand 2-1 home 1-0 away, Saudi Arabia 4-2 home 3-1 away.
Fourth round: Group B runners-up. Oman 2-2 home 0-0 away, Japan 1-1 home 1-2 away, Jordan 4-0 home 1-2 away, Iraq 1-0 home 2-1 away.
World Cup appearances: 13
Best finish: Winners (2010)
World ranking: 1
Key players: Andres Iniesta (Barcelona), Fernando Torres (Chelsea) Xavi (Barcelona), Alvaro Negredo (Manchester City)
Coach: Vicente Del Bosque (Esp)
European Group I winners: Belarus 2-1 home 4-0 away, Finland 1-1 home 2-0 away, France 1-1 home 1-0 away, Georgia 2-0 home 1-0 away.
World Cup appearances: 9
Best finish: Runner-up (1974, 1978, 2010)
World ranking: 9
Key players: Robin an Persie (Manchester United), Arjen Robben (Bayern Munich), Wesley Sneijder (Galatasaray)
Coach: Louis van Gaal (Ned)
European Group D winners: Andora 3-0 home 2-0 away, Estonia 3-0 home 2-2 away, Hungary 8-1 home 4-1 away, Romania 4-0 home 4-1 away, Turkey 2-0 home 2-0 away.
World Cup appearances: 8
Best finish: Third (1962)
World ranking: 15
Key players: Arturo Vidal (Juventus), Alexis Sanchez (Barcelona)
Coach: Jorge Sampaoli (Chi)
Qualified third in CONMEBOL: Argentina 1-2 home 1-4 away, Bolivia 3-1 home 2-0 away, Colombia 1-3 home 3-3 away, Ecuador 2-1 home 1-3 away, Paraguay 2-0 home 2-1 away, Peru 4-2 home 0-1 away, Uruguay 2-0 home 0-4 away, Venezuela 3-0 home 2-0 away.