Rops was born in Namur in 1833, and was educated at the University of Brussels. Rops's forte was drawing more than painting in oils; he first won fame as a caricaturist. He met Charles Baudelaire towards the end of Baudelaire's life in 1864, and Baudelaire left an impression upon him that lasted until the end of his days. Rops created the frontispiece for Baudelaire's Les Epaves, a selection of poems from Les fleurs du mal that had been censored in France, and which therefore were published in Belgium.
Rops's association with Baudelaire and with the art he represented won his work the admiration of many other writers, including Théophile Gautier, Alfred de Musset, Stéphane Mallarmé, Jules Barbey d’Aurevilly, and Joséphin Peladan. He was closely associated with the literary movement of Symbolism and Decadence. Like the works of the authors whose poetry he illustrated, his work tends to mingle sex, death, and Satanic images.
Rops's eyesight began to fail in 1892. He kept up his literary associations until his death.