(11bS)-8,9,10,11,12,13,14,15-Octahydro-4-hydroxy-2,6-di-9-phenanthrenyl-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.