In this short review, we briefly summarize our studies on metal-catalyzed additions of H-P(O) bonds to carbon-carbon unsaturated compounds (alkynes, alkenes, allenes, dienes and related). These new reactions provide regio- and stereoselective ways for the preparation of a variety of organophosphorus compounds. Mechanistic aspects related to the catalytic processes are discussed. (C) 2010 Elsevier B.V. All rights reserved.