Australia became the first of the 31 foreign countries to arrive in Brazil for the World Cup on Wednesday.
The Socceroos arrived in the southern city of Curitiba before transferring to another flight to Vitoria, where they will be based.
The Australians are in the tough Group B alongside World and European champions Spain, Chile and the Netherlands, who were finalists four years ago in South Africa.
"We are the underdogs," midfielder Tommy Oar said in a FIFA statement. "It will be a good opportunity for the Australian team to surprise, so this is all very exciting.
"And being in the 'soccer country' is an extra motivation, of course."
Australia enter the fray after a recent roster shake-up. Long-serving captain Lucas Neill was cut before the World Cup in favour of Mile Jedinak, which was the right call according to former Socceroos striker John Aloisi.
Crystal Palace skipper Jedinak's appointment last week was heavily backed after he was handed the captain's armband for a warm-up against Ecuador in March, but some local pundits complained that the country's most prolific scorer Tim Cahill was hard done by.
Twenty-nine-year-old midfielder Jedinak helped newly-promoted Palace exceed expectations with an 11th place finish in the Premier League, and he could similarly inspire the 59th-ranked Socceroos to play above themselves in a tough group, Aloisi said.
"I think Mile's the perfect one to take over," Aloisi told Reuters. "Anyone that can captain a Premier League side can certainly captain the Socceroos.”
"I think Mile's the perfect one to take over," - former Australian striker John Aloisi
The hard-tackling Jedinak capped 43 times for Australia and played every minute of every game for Palace until being struck down with a groin injury in their final match against Fulham.
He was rested for the Socceroos' tepid 1-1 draw in a warm-up against South Africa on Monday, with Cahill taking the reins for the farewell match in Sydney, but Jedinak is expected to be fit for the team's World Cup opener against Chile on 13 June.
"Every captain is different. I think Mile is more one that leads by example on the pitch. You can see that he's got a presence."
Up front, Australia are likely to again rely on older hands in 34-year-old Cahill and seasoned 31-year-old Japan-based striker Josh Kennedy.
Aloisi conceded Australia would be vulnerable in central defence where Neill was a stalwart for over a decade, but the team had some bright prospects out wide that might trouble their Group B rivals.
"We've got some pace out wide," said Aloisi, listing Germany-based wingers Ben Halloran and Matthew Leckie, and Tommy Oar, who plays for FC Utrecht in the Dutch top flight.
"They're both lightning quick (and) Tommy Oar's probably the best crosser we've got.
"We'll be able to cause problems with that front three."