He was the eldest surviving son of François VIII de La Rochefoucauld, 4th Duke of La Rochefoucauld, 1st duke of La Roche-Guyon and Madeleine Le Tellier, daughter of François-Michel Le Tellier, Marquis de Louvois, minister of Louis XIV and Anne de Souvré[3] Upon the death of his father in 1728, he became the 5th Duke of La Rochefoucauld.

Due to him only having daughters, he was requested, and was granted, permission by the Pope and by letters patent of the French King to transmit the ducal title to the male issue through the female line on the condition that his daughter marry a member of the La Rochefoucauld family.

Therefore, upon his death, his title passed to his grandson, Louis Alexandre de La Rochefoucauld due to salic law.

[4] On 30 July 1715, Élisabeth Bermond du Caylard (1691-1752), only child of Jacques François de Bermond du Caylard, Marquis of Toiras, and Françoise Louise de Bérard, Marquise of Vestric.

Upon the death of his eldest daughter, the estate of La Roche-Guyon was inherited by her two surviving children, Alexandre, Duke of Rohan and Alexandrine Charlotte de Rohan-Chabot.