She was the daughter of Count Charles Camille de Sainte-Aldegonde and Adelaïde Joséphine de Bourlon de Chavagne. On 8 October 1839 she married Alexandre Edmond de Talleyrand-Périgord, son of Edmond de Talleyrand-Périgord and Princess Dorothea of Courland, at the Château de Beauregard at Cellettes (Loir-et-Cher), her mother"s property.
Valentine de Sainte-Aldegonde"s passionate admirer, Anatole Demidov, attended her wedding and even helped assist the event. He offered her a diamond ornament whose magnificence caused the bridegroom worry. The next year, in 1840, Demidov briefly broke off their liaison due to financial problems, but later that same year married Mathilde Bonaparte and resumed his affair with Valentine on his first stay in Paris after his wedding.
With Talleyrand-Périgord, Valentine had six children, of whom four survived:
Clémentine Marie Wilhelmine (1841-1881) (comtesse Alexandre Orlovsky);
Charles Maurice Camille (1843–1917), 4th duke of Dino, 2nd marquis de Talleyrand;
Elisabeth Alexandrine Florence (1844-1880) (comtesse Hans d"Oppersdorff);
Archambault Anatole Paul (1845–1918), 3rd marquis de Talleyrand.
