After the introduction of the Second Empire and the marriage of Emperor Napoleon III to Eugénie de Montijo, she was appointed to the Household of the new Empress.
The ladies-in-waiting of the new Empress consisted of a Grand-Maitresse or senior lady-in-waiting, the Princesse d'Essling; a Dame d'honneur or deputy, the Duchesse de Bassano, who both attended court on grand functions; and six (later twelve) Dame du Palais, who were selected from among the acquaintances to the Empress prior to her marriage, and who alternated in pairs fulfilling the daily duties.
[4] She was also a well connected society hostess, and her "elegant and eclectic salon" in the Rue Jean Goujon was "one of the most charming centers of polite Paris".
[3] Anne d'Essling has been described as thin and fragile in her appearance, and stiff, formal and proud in her behavior, though closer acquaintances saw her as friendly and intelligent.
She belongs to the ladies-in-waiting depicted with Eugenie in the famous painting Empress Eugénie Surrounded by her Ladies in Waiting by Franz Xaver Winterhalter from 1855.