An efficient copper-catalyzed radical hydrazono-phosphorylation of alkenes with hydrazine derivatives and diarylphosphine oxides is described. The reaction provides a general and convenient method toward the synthesis of diverse β-hydrazonophosphine oxides in satisfactory yields. Based on conducted mechanistic experiments, a mechanism involving Ag-catalyzed oxidative generation of phosphinoyl radicals and subsequent addition to alkenes followed by Cu-assisted hydrazonation is proposed. Moreover, the practicability of the reaction is successfully demonstrated by its successful application on a gram scale.