Françoise Charlotte was the only child of Charles d'Aubigné and Geneviève Piètre, who were married on 23 February 1678. Because they were poor, her parents appealed to the future wife of Louis XIV, the marquise de Maintenon to help with her education. Maintenon agreed to help on the condition that Françoise Charlotte would be raised how Maintenon wished and would marry who Maintenon chose for her. As a result, Madame de Maintenon was later to make her brother's only child the heir to the Maintenon estate which she had owned since 1674.
Madame de Maintenon arranged the marriage of Françoise Charlotte with a member of the powerful House of Noailles. Madame de Maintenon arranged with Anne Jules de Noailles, the father of Madame de Gondrin, future wife of the Count of Toulouse, for the marriage of Françoise Charlotte to his son, Adrien Maurice, Count of Ayen. The wedding occurred on 31 March 1698 when she was aged 13 and he was approaching 20. During the following 21 years their marriage produced six children.
Anne-Jules, the 2nd duc de Noailles, died in 1708 and then Adrien Maurice became the 3rd Duke of Noailles with Françoise Charlotte as his duchess. Later in 1718, after the death of Madame de Maintenon, she inherited the Château de Maintenon and her aunt's wealth, as promised. Thus, from very humble beginnings, Françoise Charlotte rose to the upper levels of French society.
The Duchess of Noailles died in 1739 aged 55 but her husband lived for another 27 years, dying at Versailles at 88.