Between 1734 and 1749 she served as a Dame du Palais to Marie Leszczyńska at Versailles.

Villeroy's first husband died in 1747, at which point she purchased the impressive hôtel particulier Hôtel de Besenval.

In 1750, she married Charles II François Frédéric de Montmorency-Luxembourg, a Marshal of France and owner of Château de Montmorency.

[3] During Villeroy's residence at the chateau she allowed it to become a refuge for Jean-Jacques Rousseau.

Following the death of the Marshal-Duke of Luxembourg in 1764, Villeroy opened her Paris house to the great noble, artistic and literary names of the city, using her enormous fortune from her two marriages to become a major patron of the arts.