In last Sunday's final in Melbourne, the new world number three captured his first Grand Slam title with a four-set upset of Rafael Nadal.
Wawrinka told the Melbourne crowd he was looking forward to the tie against the weakened Serbs — as long as he survived his victory party.
"Davis Cup, it's really important for me," Wawrinka said.
"I'm really proud — it's a big honour to play for my country," he said.
Nadal, the world number one, is one of a clutch of stars missing from this weekend's opening salvoes of the venerable 114-year-old competition.
While Nadal and world number five David Ferrer skip Spain's tie with Germany in Frankfurt, Serbia must face Wawrinka's Switzerland without world number two Novak Djokovic.
The Swiss in contrast are looking strong as along with the in-form Wawrinka they boast Roger Federer.
Federer was on Wednesday confirmed for the Davis Cup World Group tie in Serbia.
The former world number one, who has slipped two places to eighth in the latest ATP rankings, was omitted from Switzerland's original team sheet.
But his presence on the hard indoor courts of Novi Sad from Friday was confirmed by competition organizers.
Later on Wednesday, Wawrinka posted a photo of himself and the 17-time Grand Slam winner with the caption: "Look who I've found in Novi Sad".
The Davis Cup is the only major trophy missing from Federer's sideboard.
This is a rare first round appearance for Federer, the last time being in 2012 when Switzerland were brushed aside 5-0 by the United States on home clay.
Serbia lost in last year's final to the Czech Republic.
Here's the schedule of games between Switzerland and Serbia:
Friday (from noon Swiss time)
Ilija Bozoljac (SRB) v Roger Federer (SUI)
Dusan Lajovic (SRB) v Stanislas Wawrinka (SUI)
Saturday (from 1pm)
Nenad Zimonjic/Filip Krajinovic (SRB) v Marco Chiudinelli/Michael Lammer (SUI)
Sunday (from 11am)
Roger Federer (SUI) v Dusan Lajovic (SRB)
Stanislas Wawrinka (SUI) v Ilija Bozoljac (SRB)