The 31-year-old aggravated a back injury during last week's Rogers Cup in Toronto, Canada.
"Stan Wawrinka felt increasing pain during the tournament in Toronto and therefore travelled back to Switzerland in order to consult with his doctor for a complete check-up".
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"I'm very sad", Wawrinka said.
Fourth-ranked Wawrinka is withdrawing from the Olympics because of injury, leaving the Rio Games without half of the ATP's top 10.
Groth - who holds the world record for the fastest serve (263.4kph) - joins compatriots Thanasi Kokkinakis, John Millman and Jordan Thompson in the Rio men's singles draw. Play begins on Saturday.
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A year later, Wawrinka triumphed at Roland Garros, becoming the only current player outside the famed Big Four (Federer, Djokovic, Nadal and Andy Murray) to win multiple majors.
Federer and Wawrinka had been due to play doubles together in Rio, triggering hopes they could rekindle their gold-medal-winning form from Beijing in 2008.
Another Swiss tennis player, Belinda Bencic, also pulled out of the Olympics.
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