Organophosphorus compounds are of high importance in organic synthesis, catalysis, biochemistry, pharmaceuticals, and material science. In this mini review, we summarize our recent studies on transition metal-catalyzed green and atom efficient transformations of P(O)-H bonds to various versatile organophosphorus compounds, including the highly regio- and stereoselective P(O)-H additions to carbon-carbon unsaturated compounds, asymmetric hydrophosphorylation reactions, and dehydrogenative coupling reactions of P(O)-H compounds with carbon-H and heteroatom-H compounds. These new reactions provide efficient, general and practical ways for the preparation of a variety of well-defined functional organophosphorus compounds. Mechanistic aspects related to the catalytic processes are also discussed.