Mademoiselle, like Madame, had a special usage in the French royal family. Its usage was restricted to the unmarried daughters of enfants de France. The senior of these, generally the eldest daughter of the king's brother, was known simply as Mademoiselle. All the others were allowed to use one of their father's titles. So if a prince was duc de Bretagne and also of Anjou, Valois, Montpensier, and Eu, his daughter might be known as Mlle de Valois, as long as Valois was not being used by another member of the family.
Probably the most famous holder of this title was
Anne-Marie-Louise d'Orléans, the very rich
heiress and
first cousin of
Louis XIV. She was, among other things, duchesse de Montpensier, comtesse d'Eu, and princesse souveraine de Dombes, but was known simply as
Mademoiselle, or as
la Grande Mademoiselle, in order to distinguish her from her cousins, the children of
Philippe de France, duc d'Orléans.