A Swiss Tennis Federation statement late confirmed the pair "have decided to not make themselves available" for the tie in Liege from .
Federation president Rene Stammbach had hinted last month during the Australian Open that the chances of seeing the pair in first round action were slim.
"I'm the first to understand that priorities change in the year after a Davis Cup victory and that it isn't that easy to get back into the fray," Stammbach said.
From Rotterdam, where hs is competing in the ATP event, Wawrinka said after reaching the semi-finals: "After long weeks of reflection, I have unfortunately decided not to play in this match.
"I have been a part of this Davis Cup squad for 11 years and this is the first time I have decided not to play."
Winner of last year's Australian Open, Wawrinka explained that 2014 had been "a very long year, rich in emotion and with some incredible moments".
But he held out the hope that he would be available for selection later in the tournament if Switzerland qualified.
"After so many years on the circuit, I have taken this difficult decision in regard to my timetable for the coming weeks," he said. "This decision only concerns the first round and we'll see later if I will return to the team."