Born to French parents in India, Worlée (1762–1835) flaunted her wealth and beauty in the salons of revolutionary Paris while married to an Englishman named Grand. Her portrait by Élisabeth Louise Vigée Le Brun in the Museum's collection (acc. no. 50.135.2) attests to her lively personality and stunning looks. She entered into a highly visible affair with Talleyrand, the brilliant statesman (and former bishop) who had become a principal figure in the emerging government. Elaborate negotiations with Napoléon, as well as with the pope, were required before the couple was allowed to marry in 1802. Upon her first official reception at the Tuileries Palace, Napoléon remarked, "I hope the good conduct of Citoyenne Talleyrand will cause the fickleness of Madame Grand to be forgotten." Madame Talleyrand rejoined, "I would not know better than to follow the example of Citoyenne [Joséphine] Bonaparte."

Talleyrand himself was particularly fond of Gérard, a student of Jacques-Louis David and a favorite of Joséphine and the court. After he was made a prince of the Empire, Talleyrand commissioned his portrait and that of his wife; both were completed by 1808. The portrait of Madame Talleyrand makes the most of her handsome grace at age forty-six. Remarkably well preserved, it demonstrates Gérard's extraordinary skills at the height of his career as an official portraitist. It is the first painting by him to enter the collection and serves as a splendid pendant to Prud'hon's 1817 portrait of Talleyrand that was also given to the Museum by Mrs. Wrightsman (acc. no. 1994.190).