She served as the principal lady in waiting, or dame d'honneur (Mistress of the Robes), to Empress Joséphine in 1804–09.

Her father was allied to the Beauharnais family, and she married Alexandre-François of La Rochefoucauld [fr; it] (1767–1841), in Paris on 9 June 1788.

As dame d'honneur it was her task to supervise the ladies-in-waiting, organize the household of the empress, decide about the visits, invitations and presentations.

[2] When Josephine was divorced from Napoleon in January 1810, Adélaïde de La Rochefoucauld applied to the emperor to be allowed to continue in her position as dame d'honneur for the next empress, Marie Louise of Austria.

Her descendants include the Dukes of Estissac and the Princes de La Rochefoucauld -Montbel (Dominique and his son Gabriel).