Organophosphorus compounds play an important role in many fields such as the organic synthesis,catalysis,biochemistry,material science,and industry.However,the traditional methods for the synthesis of organophosphorus compounds always suffer from drawbacks such as low yields and poor selectivity,and thus cannot satisfactorily meet the modern demands for more efficient applications of phosphorus compounds in material and medicinal chemistry which require the build-up of a chemical’s pool containing a variety of structurally well-defined functionalized organophosphorus compounds.During the last two decades,many groups including us have developed a couple of transition metal-catalyzed methods for the synthesis of the regio- and stereoselective organophosphorus compounds by addition to carbon-carbon unsaturated bonds (alkynes,alkenes,allenes,dienes and related).1 In this short review,we briefly summarize our studies on metal-catalyzed additions of H-P(O) bonds to carbon-carbon unsaturated compounds.These new reactions provide regio- and stereoselective ways for the preparation of a variety of organophosphorus compounds.2 Mechanistic aspects related to the catalytic processes are also discussed.