The model and singer will present Carla Bruni's Postcards from Paris on BBC Radio 2 in May.
The show, recorded in the same Paris studio where Bruni wrote her own albums, will include songs by her favourite singers including Edith Piaf, Charles Aznavour and Francoise Hardy.
She said: "When you write in French, that's what makes it Chansons Francaises. English has a lot of rhythm. Italian has a lot of melody. The good point with French is that it has a lot of description."
Her appearance is part of a series of shows on the station presented by women from the world of music and the stage including Scissor Sister Ana Matronic and Sheila Hancock who will present a show about music with a message.
She said: "I'll be playing music which I hope will make listeners think, that can possibly change their thinking - it's music with ideas, music with a message."
There will also be a two-hour special about Dolly Parton with the country superstar talking about her career and playing some of her favourite music.
Radio 2 controller Bob Shennan said: "These shows are presented by some truly wonderful names. They will give a fascinating in-depth and personal look into these specialist music genres as only Radio 2 can."