Her father was César de Bourbon, Duke of Vendôme, legitimised son of King Henry IV of France and his official mistress Gabrielle d'Estrées.

Her mother was Princess Françoise of Lorraine (1592–1669), daughter and heiress of Philippe Emmanuel, Duke of Mercœur, himself a rival of Henry IV.

They were the parents of Louis Joseph de Bourbon, a very successful military commander and a Marshal of France.

On 11 July 1643 at the Louvre, Mademoiselle de Vendôme married Charles Amadeus of Savoy, Duke of Nemours.

They had two daughters who would marry the heirs to the thrones of Savoy and Portugal, and three sons who died shortly after birth.