Bruni signed with City Models at age 19. Paul Marciano, president and creative director of Guess? Inc., came across her picture among composite cards of aspiring models and chose her to model with Estelle Lefébure in campaigns for Guess? jeans. Bruni subsequently worked for designers and fashion houses such as Christian Dior, Givenchy, Paco Rabanne, Sonia Rykiel, Christian Lacroix, Karl Lagerfeld, John Galliano, Yves Saint-Laurent, Chanel and Versace. By the 1990s, Bruni was among the 20 highest-paid fashion models, earning $7.5 million a year. While modeling, Bruni dated Eric Clapton, then Mick Jagger. On 11 April 2008, a 1993 nude photograph of Bruni sold at auction for US$91,000 (£46,098) — more than 60 times the expected price.
In 1997, Bruni quit the world of fashion to devote herself to music. She sent her lyrics to Julien Clerc in 1999, based on which he composed seven tracks on his 2000 album Si j'étais elle. In 2002, her debut album Quelqu'un m'a dit, produced by ex-lover Louis Bertignac, was released in Europe with success in Francophone countries. Three songs from the album appear in Hans Canosa's 2005 American film Conversations with Other Women, the song Le Plus Beau du quartier was used in H&M's Christmas 2006 commercial, and the title track was featured in the 2003 movie Le Divorce. In 2005, she duetted with Louis Bertignac on the song Les Frôleuses on his new album. In 2006, Bruni recorded Those Little Things an English-language translation of the Serge Gainsbourg song Ces petits riens for the tribute album Monsieur Gainsbourg Revisited. She took part in the opening ceremony of the 2006 Winter Olympics in a parade paying tribute to the Italian flag.
Her second album, No Promises containing poems by William Butler Yeats, Emily Dickinson, W. H. Auden, Dorothy Parker, Walter de la Mare, and Christina Rosetti, set to music, was released in January 2007. Her music career did not cease after becoming the First Lady. She released her third album Comme si de rien n'était (As If Nothing Happened) on 11 July 2008. The songs are self-penned except for one rendition of "You Belong to Me" and another song featuring a poem La Possibilité d'une île by Michel Houellebecq set to music. Royalties from the album will be donated to unidentified charitable and humanitarian cause.