She was the daughter of Louis II de La Trémoille, Duc de Noirmoutier, and his wife Renée Julie Aubery de Tilleport. She belonged to a cadet branch of the La Trémoille family, which held the exalted rank of "prince étranger" in France. She was married young to Adrien Blaise de Talleyrand, Prince de Chalais. Her husband, having been implicated in the duel of four against four, in which Pierre de Beauvilliers, son of the Duc de Saint-Aignan, was killed in 1663, was compelled to flee France. He died soon afterward in Spain, and Marie Anne, now widowed, established herself in Rome.