Accompanied by the Youth Music Voices choir, Walsh and Boe will debut their version of the classic Queen track on 11 May at London's Royal Albert Hall.
The official Team GB and Paralympics GB single will go on sale the same day.
"So excited to be supporting Team GB with Alfie," said Walsh. "Bring on the gold medals!"
The original track
, based around one of Brian May's most recognisable riffs, was a top 10 hit for Queen in 1985.
The lyrics have been slightly tweaked for the  
          Olympic version
 - the phrase "one man" becomes "one team" throughout the song.
Also missing is Freddie Mercury's infamous pay-off: He originally sang "Fried Chicken" instead of the title during the fade out.
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Walsh, who has enjoyed massive chart success with her fellow Girls Aloud stars, is currently playing Princess Fiona in Shrek The Musical at London's Theatre Royal.
"It's a huge honour to sing One Vision for Team GB with Kimberley," said Boe, who was acclaimed for his performance in the 25th anniversary concerts of Les Miserables.
"Being a massive Queen fan, I was very excited about recording the track - I hope everyone likes it."
The Duke and Duchess of Cambridge will join the official Team GB launch party, Our Greatest Team Rises, at the Albert Hall next week, alongside a host of British Olympians.
Girls Aloud star Kimberley Walsh and leading tenor Alfie Boe are joining forces to sing on One Vision, the official single for Team GB.