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 Dame du Palais, who were selected from among the acquaintances to the Empress prior to her marriage, and who alternated in pairs fullfilling the daily duties. As Grande-Maitresse, Anne d'Essling was first in rank of all female courtiers. It was her task to supervise all the other ladies-in-waiting and their schedule, and receive all applications from people wishing to be given an audience with the empress. In practice, however, she normally delegated this to the next in rank, dame d'honneur Pauline de Bassano. Alongside the dame d'honneur, it was also her task to be present at the side of the empress at all grander public representational state occasions, and she was as such a well known public figure. She did not attend court daily but only on state functions and important events, such as state dinners. She did, however, make a formal visit to the Tuilieres each day when Eugenie was in Paris, to learn the empress' wishes, and then leave again. It was noted how she often saved the empress from making a blunder with her naming list, as the functions Eugenie was required to host was so large that she often forgot the names of her guests. She accompanied the emperor and empress on the state visit to Great Britain in 1857. 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". Anne d'Essling has been described as thin and fragile to her appearance, and stiff, formal and proud to her behavior, though closer acquaintances saw her as friendly and intelligent. She was described in retrospect: She remained in service until the fall of the monarchy and was present with the Empress in the Tuileries Palace during the fall of the Second Empire in 1870. She then retired from high society life.
