The 51-year-old was confirmed as Australia's new head coach until the end of the 2026 World Cup on Monday, three days after Graham Arnold stepped down.
"I am extremely honoured to be given this opportunity to lead the Socceroos as head coach," Popovic said in a statement.
"It's a role that comes with great responsibility, and I'm deeply grateful for the opportunity.
"This is undoubtedly a very proud moment for myself and my family.
"To be entrusted with guiding our national team is a privilege that I do not take lightly.
"I want to express my sincere gratitude to Football Australia for their confidence in my abilities. Their trust motivates me to give my absolute best in this role."
Popovic has been out of work since leaving Melbourne Victory this year but will be thrust straight into the cauldron of World Cup qualification.
With their hopes of automatic qualification under threat following Arnold's last two games in charge, Popovic will be charged with resurrecting the Socceroos' campaign with little build-in towards his first game.
The former Western Sydney and Perth Glory boss will be in the dugout against China in Adelaide on October 10, before a trip to take on Japan on October 15.
Australia are winless through their first two games of the third stage of qualifiers.
"We have moved swiftly to secure the best possible candidate for this crucial role," said FA chief executive James Johnson.
"Our prompt action reflects our commitment to maintaining the momentum and success of the Socceroos program, especially as we are at the beginning of the critical third round of AFC Asian Qualifiers."
Popovic will have to nominate a long list of players in the next week for those two fixtures, and it remains unclear how many of Arnold's staff intend to stick around for life under their new manager.
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