Like the other women Impressionists, Gonzalès could not attend the École des Beaux-Arts, the prestigious art school as women students were forbidden. Fortunately, her upper-class status provided her with the financial resources to pursue her artistic career and, after training for a while with Charles Joshua Chaplin, a society painter connected to the state-funded French Academy. In 1869, she met the avant-garde painter, Édouard Manet. By all accounts, he was very drawn to Gonzalès and, in addition to forging a friendship with her, took her on as his student - the only student he ever accepted, although by all accounts the arrangement was not particularly formal. He had met another one of the women Impressionists, Berthe Morisot, and, by all accounts, was equally taken with her, also painting her portrait on multiple occasions as he had Gonzalès's but never taking her on as a student.

Either way, having the support of Manet was no small thing as he was a major figure in the avant garde art scene; he had challenged the artistic establishment repeatedly, submitting daring, unconventional works like Le Déjeuner sur l'herbe (Luncheon on the Grass, 1862-3) and Olympia (1864) to the official Salon only to have them rejected but gaining public and critical support in the process. Gonzalès never exhibited her work in any of the Impressionist exhibitions but, because of her painting style, she is identified with the group. She and her husband Henri Charles Guérard (the fairly famous and celebrated French engraver and lithographer) were friends with many painters, including Paul Cézanne.

Her career and life were tragically brief, however, as Gonzalès died in 1883 at age 34 from complications in childbirth, and therefore did not have the opportunity to continue developing her work. A retrospective of her work that included around 90 paintings and pastel drawings, was held in 1885 at the Salons de la Vie Moderne in Paris.