They may have lost 3-0 to Brazil in the recent Confederations Cup final but, with the likes of Sergio Ramos, Andres and Iniesta and Sergio Busquets in their intimidating line-up, they are among the favourites at the 2014 World Cup.
The Netherlands, meanwhile, cruised through qualifying and boast names like Manchester United star Robin van Persie in their side.
Chile are lowest-ranked of all three of Australia's opponents at No.15 but are still well above the 59th-ranked Socceroos, the lowest-ranked side in the 32-team tournament.
The South Americans recently impressed in a 2-0 friendly win over England and have Barcelcona star Alexis Sanchez on their roster.
Socceroos coach Ange Postecoglou said he was looking forward to the challenge of meeting such high quality opponents.
"We're going to see some good football in our group, that's for sure,'' Postecoglou told SBS.
"There's some great footballing nations and our job is to play our part. It's an enormous challenge for us but for a nation like ours that's exactly what we want.
"We've got a chance to make some headlines when the World Cup comes around.''
Postecoglou said the three matches would serve as invaluable experience for his charges.
"We know what Spain are like and the Dutch have always played good football and in this qualifying campaign Chile have been outstanding,'' he said.
"So there's going to be some real footballing challenges ahead of us. We want to keep growing and keep getting better and that's our measures.''
The new coach said his players would all be relishing the opportunity to play some of the world's top nations on the greatest stage of all even though no-one would be expecting them to do well.
"There wouldn't be one of our players who wouldn't be looking forward to this immensely,'' he said.
"To play the world's best teams that's why you go to a World Cup.
"Everyone will be writing us off in this group, which is I think is logical.
"But from our perspective we've some great opportunities to show the world we can play some good football against the best nations in the world.
"Our group looks the most difficult group but I hope it's the group that plays the best football and we'll play our part in that.''
Defending champion Spain will play its opening 2014 World Cup game against the Netherlands, a repeat of the ill-tempered 2010 final, while host Brazil faces a relatively easy path to the knockout stage.
Argentina, champion in 1978 and 1986, first plays Bosnia-Herzegovina, the only World Cup newcomer among the 32 teams. After that game at the Maracana stadium in Rio de Janeiro, the Argentine team of four-time world player of the year Lionel Messi then plays Iran and finally Nigeria. In six previous World Cup encounters, Nigeria has beaten Argentina just once.
Argentina will be heavily favored to come out top of its Group F. If so, it could find either Switzerland or France in its way in its first knockout game. Those European nations will be hoping to come out on top of their Group E that also includes Ecuador and Honduras.
The Spain-Netherlands match is on June 13, a Friday. When they met at the 2010 final, referee Howard Webb showed a record 14 yellow cards two leading to red for the Netherlands' John Heitinga.
England's first match will be in the heat and humidity of the Amazon basin, which coach Roy Hodgson was anxious to avoid. That night game in the Amazon city of Manaus pits the 1966 champion against Italy, a four-time winner.
Both will have to play their best to advance from Group D, since it also includes 2010 semifinalist Uruguay and Costa Rica.
"It's a tough group, there's no doubt about that. In Italy and Uruguay it's almost as though we have got two number one seeds in our group. We know how good Italy are because we lost to them in the quarterfinals at the Euros. The game is going to be tough from a climate point of view for both teams,'' said Hodgson.
England could also face hostility from the home crowd after the city's mayor said he did not want the English in Manaus because they complained about the venue's climate.
The United States was drawn into a tough group with Germany, the winner in 1954, 1974 and 1990, as well as Cristiano Ronaldo's Portugal and Ghana, a quarterfinalist in 2010. The U.S. is coached by former Germany striker Jurgen Klinsmann.
Brazil starts its campaign for a sixth World Cup title with an opener against Croatia. Mexico and Cameroon are also in the group.
Colombia, Greece, Ivory Coast and Japan are in Group C, with Uruguay, Costa Rica, England and Italy in a strong Group D.
One of the easiest groups on paper looked to be E, with Switzerland, Ecuador, France and Honduras.
Russia, host of the next World Cup, is in Group H with Belgium, Algeria and Korea.
World Cup Group A: Brazil, Croatia, Mexico, Cameroon.
World Cup Group B: Spain, Netherlands, Chile, Australia.
World Cup Group C: Colombia, Greece, Ivory Coast, Japan.
World Cup Group D: England, Italy, Uruguay, Costa Rica
World Cup Group E: Switzerland, Ecuador, France, Honduras
World Cup Group F: Argentina, Bosnia-Herzegovina, Iran, Nigeria.
World Cup Group G: Germany, Portugal, Ghana, United States.
World Cup Group H: Belgium, Algeria, Russia, Korea.
-AAP
