Oscar-winning actor Richard Dreyfuss, singer James Blunt , Tennis ace Johanna Konta, TV presenter Kelly Brook and actress Caroline Quentin will also show off their skills with a whisk in the Channel 4 show, for Stand Up To Cancer.
The five-part series will see Prue Leith and Paul Hollywood return to judge the bakes this spring.
Style expert Tan France, 36, originally from Doncaster, is one of the "fab fave" members of the Queer Eye team, whose Netflix show documents them helping to turn around the lives of people who are stuck in a rut.
He is also due to co-host an upcoming new Netflix show called Next in Fashion with Alexa Chung.
Bake Off hosts Noel Fielding and Sandi Toksvig will be on hand "to provide tea and sympathy" in the famous tent.
Documentary maker Louis Theroux, TV presenters Alex Jones, Carol Vorderman and Scarlett Moffatt and TV judge Rob Rinder will be hoping to demonstrate their baking prowess.
Comedians Mo Gilligan, Russell Howard, Joel Dommett and Jenny Eclair, This Morning's Alison Hammond, Love Island's Ovie Soko, ex-EastEnders actress Patsy Palmer, YouTuber Joe Sugg and actor James Buckley are also on board.
-> Tan France’s journey from suffering racist bullying in Doncaster to starring in Queer EyeEach episode will see four celebrities battle it out over three rounds - the Signature, the Technical and the Showstopper - in a bid to be crowned Star Baker.
Sarah Lazenby, head of formats and features at Channel 4 said: "The Great Celebrity Bake Off is a key ingredient in our Stand Up To Cancer recipe.
"We've seen the power of using comedy and entertainment to bring awareness and raise millions of pounds to fund pioneering cancer trials.
"We hope viewers will enjoy this year's line-up of famous bakers."
She quipped: "There's never a dough moment as each bring something fresh and exciting to the tent."
Stand Up To Cancer is a joint national fundraising campaign from Cancer Research UK and Channel 4.
It has raised over £62 million, funding 52 clinical trials and projects involving 11,000 cancer patients.
Donate at channel4.com/su2c or sign up to fundraise at standuptocancer.org.uk