Following the facile synthesis of a novel phosphine oxide compound, (diphenylphosphinoyl)phenylmethanol (1), this compound was employed as a ligand in the rhodium-catalyzed hydroformylation of alkenes, with good conversions and regioselectivities. This ligand was partially resolved using an enzyme, and enantioselective hydroformylation was carried out with the addition of a rhodium(I) complex. The rhodium(I) complex containing ligand 1 was not isolated, although it was subjected to low-temperature NMR studies.