The composer Charles Gounod became Édouard's brother-in-law (and lifelong friend) when he married Juliette's sister Anna.

[2] During a stay in England, from 1848 to 1851, Dubufe discovered the great English portrait painters, who he would seek to emulate.

His official career as a portrait painter began in 1853 with portrayals of Emperor Napoléon III and the Empress Eugénie.

Dubufe continued to enjoy great success with the aristocracy, receiving a commission from the Emperor to paint the Congress of Paris in 1856.

In April 1866, the journal L'Événement [fr] ran an article by Émile Zola that criticized Dubufe's qualifications for acting as a judge at the Salon and suggested that he belonged to academic cliques that compromised his judgment.