In 1514, the earldom of Vendôme was raised to a duchy-peerage in favour of Charles de Bourbon.

By 1527, Charles had outlived the dukes of Alençon and of Bourbon, and he became first prince of the blood, the head of the most senior line of the dynasty after the royal family.

It was founded by César de Bourbon (1594–1665), the legitimized son of Henry IV and his mistress, Gabrielle d'Estrées.

Born in 1594, César de Bourbon was created Duke of Vendôme by his father, the former holder, in 1598.

After the creation of 1598, the title continued to be used by César de Bourbon's family for over a century.