A highly stereoselective catalytic method for the preparation of structurally diverse P-stereogenic oxides has been developed. The approach relies on the ability of rhodium complexes derived from an enantiopure P–OP ligand to kinetically resolve racemic α,β-unsaturated phosphane oxides by hydrogenation of the C═C motif and formation of highly enantioenriched (or even enantiopure) P-stereogenic oxides. The practicality of the methodology has been demonstrated by the preparation of potentially functional P-chiral molecules for catalytic enantioselective synthesis.