Following her father-in-law's death, her husband succeeded as Prince of Condé, a purely honorary title, but one of the highest ranking in France.

At the age of fifteen, she was engaged to Henri Jules, Duke of Enghien, the only surviving child of the famous military commander the Grand Condé.

Henri Jules was his heir and prior to his succession to the purely honorary title of Prince of Condé, was styled the Duke of Enghien and was addressed Monsieur le Duc.

The marriage ceremony took place at the Palais du Louvre on 11 December 1663 with Louis XIV of France and the rest of the royal family in attendance.

In 1708, when her cousin Charles IV, Duke of Mantua died, being his heiress, Anne Henriette became the Princess of Arches in her own right.

The next year, Anne's husband died in Paris on 1 April 1709, aged 65, making her son, Louis, the next Prince of Condé.