The 20-year-old Liverpool left back was born in Australia to British parents and moved to England when he was 14, going on to represent the country at under-17, under-19 and under-21 levels.
Smith will be sidelined for several weeks after injuring his knee while on loan at Swindon Town last week, though, suggesting his call-up is a bid to secure his services for the Socceroos.
"Brad's a player we have been monitoring since I've been in the job and he plays in a position where we don't have a great deal of depth. He plays left back and left side and he's quick," Postecoglou said in a news release.
"Brad's played for the England under-21s as recently as a couple of months ago but he's very committed to playing for Australia and after having a chat to him we are really keen to get him in the green and gold and give him an opportunity."
Smith was one of four uncapped players in Postecoglou's first squad since the World Cup, where Australia lost all three matches but gained some credibility with competitive performances against Chile and the Netherlands.
They play friendlies against World Cup quarter-finalists Belgium on Sept. 4 in Liege and Saudi Arabia in London four days later as they continue preparations for the Asian Cup, which takes place in Australia next January.
The other uncapped players are Aston Villa's versatile Chris Herd, FC Zwolle defender Trent Sainsbury and Bailey Wright, the Preston North End central defender who was included in the World Cup squad but never got a game.
Bayer Leverkusen striker Robbie Kruse, who missed the World Cup because of injury, returns to the squad, which includes 12 players who went to Brazil, including striker Tim Cahill and skipper Mile Jedinak.
Squad: Terry Antonis, Joshua Brillante, Tim Cahill, Jason Davidson, Ben Halloran, Chris Herd, Mile Jedinak, Tomi Juric, Robbie Kruse, Mitchell Langerak, Matthew Leckie, Massimo Luongo, Mark Milligan, Tommy Oar, Mat Ryan, Trent Sainsbury, Brad Smith, Carl Valeri, Alex Wilkinson, Bailey Wright.
(Reporting by Nick Mulvenney, editing by Greg Stutchbury)
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