The reactions of phosphinylidene-containing compounds with unactivated unsaturated hydrocarbons are reviewed. The review is organized by phosphorus-containing functional group types. Free-radical and metal-catalyzed additions of R(1)R(2)P(O)H to alkenes, alkynes, and related compounds, deliver functionalized organophosphorus compounds RP(O)R(1)R(2), including H-phosphinates, phosphinates, tertiary phosphine oxides, and phosphonates. The review covers the literature up to February 2008.