The Socceroos will play co-hosts the USA, Paraguay and a European playoff qualifier in group D in next year's finals, after dodging big guns Argentina, Spain, France and England in the draw.
Speaking immediately after the draw, Popovic said he was "satisfied" with Australia's group.
That comment seemingly drew the ire of former star striker Donovan.
"I watched the Aussie coach's interview after the draw and it was really interesting," Donovan said on Fox Sports.
"It was unique. Because most coaches say all the same stuff you're expecting like 'oh, it's a difficult draw, this is going to be so hard - and his first comment was: 'we're satisfied'.
"And I was like: 'really? Are you?'
"And he just had this smugness about him and I'm like 'alright, I can't wait. I wish I was on the field - like, I wanna play these guys'."
"They're a solid team, they're hard to play against, this is not going to be some blowout, whatever, but it's a team I think we should beat."
Donovan then doubled down in the segment, with fellow ex USA players Cobi Jones and Brad Guzan.
He predicted the USA to top the group, yet-to-qualify Turkey to come second and Paraguay to finish third - with Australia fourth.
"Thanks for coming, Aussies and your smug coach - you can get back on the Qantas airplane and head back home, pal," he quipped.
Donovan isn't the first US pundit to write off the Australians, or consider the group an easy one for the locals.
On the day of the draw, former US player Alexi Lalas said: "If you believe in the soccer gods, you should be thanking them.
"I don't want to say it's an easy group, but we also have to be realistic with what we got here."
CBS pundit Mike Grellas described the Australia fixture as a "lay-up" while former international Charlie Davies called the group "a dream scenario".
At the time, Popovic was unsurprised by local pundits backing their team but made it clear the Socceroos believed they could get through the group stage and could head with a lot of optimism and confidence.
"Anyone that underestimates us, I think will get a rude shock when it comes to those group games," he said last Saturday.
The Socceroos suffered a 2-1 loss to the USA in a spiteful friendly in October.
