Popovic has picked Joe Gauci as goalkeeper ahead of usual skipper Mathew Ryan for Thursday night's World Cup qualifier against China in Adelaide.
Ryan, who has captained the Socceroos since October 2019, is on the substitutes bench.
Ryan started in goal in Australia's most recent two World Cup qualifiers last month - a scoreless draw in Indonesia and a shock 1-0 loss to Bahrain on the Gold Coast.
Those results to open the third phase of qualifying for the 2026 cup in North America prompted Graham Arnold to quit as coach.
Popovic was appointed as Arnold's replacement on September 23.
📋 Here's Tony Popovic's first — Subway Socceroos (@Socceroos) #Socceroos XI to face China PR tonight! 👊🇦🇺 v 🇨🇳 - 10.10.24 - 8:00pm AEDT📱💻📺 10, 10 Play, Paramount+#AUSvCHN pic.twitter.com/4miRY1ZMBnOctober 10, 2024
Ryan, a veteran with 95 Socceroos caps, has struggled for recent game time at club level in Italy's Serie A with Roma with Popovic preferring Aston Villa's Gauci in goal.
The Australians are fifth in the six-nation group, ahead of only China, who have conceded a dozen goals in losing both games of the fresh qualifying phase.
After hosting China, the Socceroos face a demanding away trip to play unbeaten group leaders Japan next Tuesday night.
Eight games remain in the qualifying phase with the top two nations securing direct passage to the '26 cup and the third-placed nation pitched into another qualifying round.
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