His younger brother, Pierre-Édouard, and his nephew and namesake, Charles Edouard Frère, were also painters.
The son of a Paris music publisher, Frère studied at the École des Beaux-Arts under Léon Cogniet and Camille Roqueplan.
His exhibits at the Salon in subsequent years were nearly all Orientalist paintings as a result of several journeys to Africa and the Near East.
Around 1851, he undertook a further journey to the Near East, visiting Malta, Greece, Egypt and Turkey becoming one of the few artists to paint Beirut, Damascus and Palmyra.
[1] In 1869, he once again travelled to the Egypt, now as a member of Empress Eugénie's party, for the opening of the Suez Canal.