Popyrin has declared himself raring to go for the looming World Group qualifying stages in Europe after surging to his maiden second-week appearance at a grand slam at the US Open in New York.
The 25-year-old thwarted Novak Djokovic's quest for a record 25th grand slam crown en route to the last 16, making it six top-20 scalps from his past nine matches for Popyrin.
The Montreal Masters champion admitted he was "knackered" and in need of a few days' break but nothing will stop him from joining Open stand-outs Alex de Minaur and Jordan Thompson for the group stages in Spain from September 10-15.
Last crowned champions in 2003, Australia have lost the past two finals to Canada and Jannik Sinner's Italy respectively and are hell bent on going one step further in 2024 to lift the age-old trophy.
"It's very important. We really want to win one. It's top of our priority all year long," Popyrin said before departing Flushing Meadows.
"So we've always made ourselves available. Nothing is going to change now that I have played more matches than I think anybody would have imagined this summer.
"I'm going to take a few days off and then fly up to Valencia and get with the team.
"It's a huge opportunity for us to test ourselves against the best teams in the world, best countries in the world.
"We're back-to-back finalists in Davis Cup, so we've got to hold ourselves up and show what we're made of there."
Seeded second, Australia have been drawn in Group B alongside Czech Republic, France and Spain.
The top two teams from each pool will qualify for the eight-nation knockout stages in Malaga from November 19-24.
De Minaur, Australia's long-time Cup spearhead, saluted Popyrin's stunning emergence from outside the world's top 60 barely a month ago to grand slam challenger and new world No.23.
The two 25-year-olds were both born and raised in Sydney while also spending much of their teenage years honing their game in Alicante.
"Alexei, I've grown up with him, and he's one of the best blokes out there," de Minaur said.
"So the fact that this is happening to him, I think everyone in Australia couldn't be prouder and couldn't be happier for him.
"He's always had this big game but the way I'm seeing it is, in his mind, it's clicked.
"It's clicked exactly his game style - what he wants to do every time he steps on court.
"And he believes. So much in this game, it's about belief.
"I felt myself I struggled with that belief to take it to the next level, and I'm just happy to see 'Popyrin' breaking through those barriers and in, in my eyes, once you break through, you never look back.
"I think we're going to see some really, really great things from Pop."
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