After the death of her brother Jean Louis Charles d'Orléans, Duke of Longueville in 1694 she succeeded him as sovereign Princess of Neuchâtel, although she remained a prominent member of the French royal court.

Descended from Jean d'Orléans, illegitimate son of Louis I, Duke of Orléans, she was known as Mademoiselle de Longueville prior to her marriage.

At an early age she was involved in the first Fronde, of which her father and stepmother, Anne Geneviève de Bourbon, were leaders.

When he died in 1659, leaving her childless, the rest of her life was mainly spent in contesting her inheritance with her stepmother.

[2] She was the muse for Jean Loret's Muse historique (1650, 1660, 1665), a collection of weekly gazette burlesque reporting on the news of Paris society and the court of Louis XIV in the form of letters to Marie d'Orléans-Longueville which are considered an early example of French journalism.