The Socceroos are expected to have little trouble disposing of Asian minnows Jordan, Tajikistan, Kyrgyzstan, and Bangladesh during the first part of their World Cup qualifying campaign.
But Postecoglou will demand that Australia's best talent from around the world must front up for these matches.
Postecoglou says the days of old when Socceroos stars could pick and choose which matches they wanted to play were well and truly over.
"There wouldn't be a player who wouldn't walk here if I asked them to," Postecoglou said in Perth on Thursday.
"This is playing for your country in a World Cup game at home. Getting releases for players is the last thing on my mind.
"The players feel like we're on a good path and some good times are just around the corner, and they don't want to miss out.
"The ones who weren't in the Asian Cup squad, I'm sure they would have been watching it on telly or in the stadium thinking they want to be a part of that next time.
"To do that, you have to put your hand up every time we play. The players have been fantastic so far."
Australia is the only team in its group ranked inside the top 100.
Jordan is the next highest at 103, with Tajikistan at 143 and Bangladesh way back in 167th.
Nevertheless, Postecoglou has vowed to unleash full-strength sides against the Asian minnows.
"These games will be used to put our strongest teams out there, and make sure we win and play well and keep progressing our football," Postecoglou said.
"We'll get opportunities to keep broadening our base, but we won't experiment too much in these games.
"As Asian Champions we have our own standards we want to maintain and improve. These are serious games because qualification for the World Cup is at stake.
"We won't compromise on making sure we put our best team out there every time we play in these games."
The Socceroos kick off their campaign in Kyrgyzstan on June 16, before taking on Bangladesh in Perth on September 3.
Postecoglou admits his team has plenty of work to do on the logistics front: "Some people got some geography lessons last night, found out some countries they probably didn't think existed," Postecoglou said with a smile.
"But I'd much rather this format than playing endless friendlies."
