A Craig Goodwin cracker, unlikely hero Lewis Miller's header, and a goal from debutant Nishan Velupillay ensured Popovic's tenure started in triumph.
The Socceroos were shaken when conceding the opening goal to China's Xie Wenneng in the 20th minute of Thursday night's cup qualifier in Adelaide.
But the oft-pilloried Miller - who had been banished since February after his personal horror show at the Asian Cup - equalised in added time.
Unlikely hero Lewis Miller celebrates scoring from a Craig Goodwin free kick against China. (Matt Turner/AAP PHOTOS)
Goodwin then produced a top-shelf stunner in the 57th minute to deliver Australia's first win from three games in this round of qualifying for the '26 cup.
Goodwin was found in space by an insightful pass from Jackson Irvine, who captained the Socceroos as Popovic opted for Joe Gauci in goal instead of regular 'keeper Maty Ryan.
Goodwin took a series of deft touches and, from about 20 metres, loaded on his left foot and fired into the net en route to player-of-the-match honours.
The win lifts Australia to third spot in the group of six nations, with four points - five games remain in this phase of qualifying for the 2026 cup in North America.
Popovic's charges next meet unbeaten group leaders Japan, who have banked six points from two games, in Saitama on Tuesday night.
Craig Goodwin. It's what he does 🔥— Subway Socceroos (@Socceroos) He scores a beauty from distance in front of his hometown to put us in front 🚀🎥 @10FootballAU #AUSvCHN #Socceroos pic.twitter.com/nNJI0hGeD9October 10, 2024
The top two nations secure direct passage to the '26 soccer showpiece and the third-placed nation is pitched into another qualifying phase.
Popovic was appointed when Graham Arnold quit as coach after a scoreless draw in Indonesia and a shock 1-0 loss to Bahrain on the Gold Coast in last month's qualifying window.
Popovic made a pre-game impact by benching Ryan, who has been captain since October 2019, in favour of Gauci.
The new boss also summoned Miller, who had been on the outer since giving away a penalty and a free kick which resulted in South Korean goals in Australia's 2-1 quarter-final loss at the Asian Cup last February.
Popovic's show of faith was rewarded in the 47th minute when Miller, despite being sandwiched by Chinese defenders, latched onto a Goodwin free kick and headed the equaliser.
After halftime, South Australian Goodwin sent the parochial 46,291-strong Adelaide Oval crowd - the largest attendance at a Socceroos game in the state - into raptures with his sublime strike.
And substitute Velupillay iced the win in the 92nd minute with a coolly-taken right-footer from six metres out.Â
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