Born in Paris, Rophé studied as early as 1974 at the Conservatoire de Paris, first studying the flute. He won second prize of a competition of young conductors at the Besançon International Music Festival in 1988.
From 1992, he worked with Pierre Boulez and David Robertson within the Ensemble InterContemporain. On 19 May 1998, Rophé conducted the premiere of Salvatore Sciarrino's opera Luci mie traditrici at the Schwetzingen Festival. He recorded in 2002 Thierry Escaich's Concerto pour orgue with organist Olivier Latry. The recording won the Diapason d'Or de l'Année award. The same year, he recorded Intrada by Éric Tanguy with the Orchestre national de France at the Salle Olivier Messiaen of the Maison de la Radio during the Festival "Présences 99" (2002). He conducted in 2005 the premiere of Michael Mantler's Concerto for Marimba and Vibraphone with the hr-Sinfonieorchester.
From 2006 to 2009, Rophé was musical director of the Orchestre Philharmonique de Liège. In 2011, he premiered Akhmatova, Bruno Mantovani's last opera, at the Paris Opera. He conducted Phosphor, a concerto for percussion and orchestra by Johannes Schöllhorn, played by its dedicatee Pascal Pons, in October 2006 for the French premiere at the Musica Festival in Strasbourg and the Belgian premiere in Liège. They recorded in 2007 Tout un monde lointain... for cello and orchestra by Henri Dutilleux, with soloist Marc Coppey.
In September 2014, Rophé became musical director of the Orchestre national des Pays de la Loire. In 2016, he recorded with the orchestra works by Dutilleux to mark the composer's centenary, including Le Loup, 3 Sonnets de Jean Cassou and Fille du Diable. He conducted the BBC's celebration of the centenary called Total Immersion Day: the Magical Soundworld of Henri Dutilleux, selecting five pieces: Tout un monde lointain ..., Métaboles, a concerto for orchestra, the string quartet Ainsi la nuit, The Shadows of Time for three children's voices and orchestra, and Le temps l'horloge for soprano and orchestra.
Rophé was re-appointed as orchestra director in 2017 for three years. He premiered on 10 March 2017 with the Orchestre Philharmonique de Radio France the second symphony Âme ("soul") by Philippe Schoeller, written on a commission by Radio France.