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The poet Charles-Albert Demoustier, who met her in 1784, was inspired by her in creating the character Emile in his work Lettres a Emilie sur la mythologie (1801).

In 1791 she exhibited for the first time in the Salon de Paris, displaying her mythology-inspired picture Psyche faisant ses adieux a sa famille. Another of her paintings of this period, L'Innocence entre la vertu et le vice, is similarly mythological and reveals her feminist interests-in this picture, vice is represented by a man, although it was traditionally represented by a woman. In 1793, she married the lawyer Pierre-Vincent Benoist.

Her work, reflecting the influence of Jacques-Louis David, tended increasingly toward history painting by 1795. In 1800, she exhibited Portrait d'une negresse in the Salon. Six years previously, slavery had been abolished, and this image became a symbol for women's emancipation and black people's rights. This picture was acquired by Louis XVIII for France in 1818.

Elisa Bonaparte, Emperor Napoleon's sister and Duchess of Lucca, painted by Marie Guilhelmine Benoist about 1805. An important commission, for a full-length portrait of Napoleon Bonaparte- premier Consul Francais in this period - was awarded to her in 1803. This portrait was to be sent to the city of Ghent, newly ceded to France by the Treaty of Lun?ille in 1801. Other honors came to her; she was awarded a Gold Medal in the Salon of 1804, and received a governmental allowance. During this time she opened an atelier for the artistic training of women.

Her career was harmed by political developments, however, when her husband, the convinced royalist count Benoist, was nominated in the Conseil d'Etat during the post-1814 monarchy come-back called the Bourbon Restoration. Despite being at the height of her popularity, she has to abandon her career, both painting and exposing, due to her devoir de reserve and the strongly enforced conservatism of the reactionary regime.