After Louis XIV's marriage to Maria Theresa of Spain on 9 June 1660, Queen Anne turned her attention to the marriage of Philippe. He had previously been encouraged to court his older cousin the Duchess of Montpensier, eldest daughter of Gaston and his first wife Marie de Bourbon. Known as Mademoiselle at this time, she had an immense private fortune and had previously rejected suitors such as Charles II of England. Born in 1627, she was the sole heiress of her mother who died in childbirth. Mademoiselle declined the union, complaining that Philippe always stayed near his mother as if he was "like a child". Mademoiselle instead remained unmarried.
Philippe would marry instead another first cousin, Princess Henrietta of England (youngest child of Queen Henrietta Maria and the dead Charles I of England) on 31 March 1661.
Mademoiselle was in attendance with various other members of the court.
Mademoiselle was the godmother of Philippe and Henrietta's youngest child, the Mademoiselle de Valois, born in 1670. Once again at Henrietta's death in 1670, Louis XIV asked if Mademoiselle wanted to fill "the vacant place" that had been left by Henrietta, a suggestion she declined.