Catalytic difunctionalization with the direct activation of (O)P-H bonds has been recently established as a potentially robust platform to generate valuable organophosphorus compounds. In terms of 1,3-enynes, despite of the various catalytic methods developed for hydrophosphorylation, the radical-mediated hetero-functionalization of two different atoms has been less explored. In this study, we disclosed an electrochemically induced hydroxyphosphorylation of 1,3-enynes for the construction of phosphinyl-substituted propargyl alcohols. The system involves the direct activation of both arylphosphine oxides and oxygen in ambient air with no external metal or additive needed. The use of electrochemistry ensures the regioselective, atom-economic and eco-friendly for the difunctionalization process. This strategy highlights the advantages of mild reaction conditions, readily available starting materials and broad substrate scope, showing its practical synthetic value in organic synthesis.