Rops was the son of a textile manufacturer. After his first artistic training at the Academy of Namur, his hometown, he relocated to Brussels at the age of twenty and briefly attended the University. His early work on student periodicals attracted the attention of publishers, and he began to produce illustrations, contributing some of his finest lithographs to the satirical journal Uylenspiegel in 1859–60. In 1862 he went to Paris, where he met the etchers Félix Bracquemond and Jules Ferdinand Jacquemart. His activity as a lithographer ceased about 1865, and he became a restless experimenter with etching techniques. Rops met Charles Baudelaire in Paris in 1864, towards the end of the poet's life, and Baudelaire left an impression upon him that lasted until the end of his days. Rops created the frontispiece for Baudelaire's Les Épaves, a selection of poems from Les Fleurs du mal that had been censored in France, and which therefore were published in Belgium.
His 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 Péladan. He was closely associated with the literary movement of Symbolism and Decadentism. Many of Rops’s etchings are erotic or pornographic in tone and depict an imaginary underworld or subjects of social decadence. Rops was a printmaker of brilliant technique and original content whose handling of drypoint marks him as one of the masters of the medium. He was also one of the first modern etchers to revive the neglected medium of soft-ground etching.