(11bS)-4-Hydroxy-2,6-bis(2,3,4,5,6-pentafluorophenyl)-4-oxide-dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin is a chiral phosphoric acid catalyst for a variety of enantioselective transformations, especially for carbon-carbon and carbon-heteroatom bond-forming reactions.