The ten-part series will consist of conversations between two famous faces, instead of being led by an interviewer.
Among the celebrities taking part are Stephen Fry, Joanna Lumley, Caitlin Moran and Brigitte Nielsen.
Sky Arts' channel director James Hunt said: "This series is a true who's who of the great and the good in their respective fields.
"This style of interview is unusual and revealing, largely because each contributor is set at ease by a sense of shared experience, which makes for a very illuminating and unguarded discussion. It's a fascinating series, and we're delighted to have it on Sky Arts."
Fry will converse with Bill Wyman, while Lumley will spend her hour with Melvyn Bragg. Moran will talk to novelist Fay Weldon and Nielsen will be involved in a conversation with Britt Ekland.
Elsewhere, GQ editor Dylan Jones will talk to George Lamb, actor Leslie Phillips will speak to Bee Gees member Robin Gibb and musician Sir Tim Rice will have a conversation with cricketer Sir Ian Botham.
The remaining three episodes will feature Olympics champion Lord Sebastian Coe talking to sports reporter Gary Newbon, artist Sir Peter Blake in conversation with director Ken Russell, and actors Paul McGann and Charles Dance having a discussion.
Sky Arts also recently commissioned a drama about Watergate starring Harry Shearer and the second series of Fame In The Frame is currently airing.
Living The Life will begin on November 6 at 8pm on Sky Arts 1.