AbstractCopper(II) on 4 Å molecular sieve was found to be an efficient heterogeneous catalyst in the addition of different H-phosphinates and secondary phosphine oxides to phenylacetylene. All hydrophosphinylation reactions were completely regioselective, as only β-isomers were formed, and the E-alkenylphosphinates and E-alkenylphosphine oxides were synthesized in moderate to excellent yields. The catalyst could be reused multiple times in the reaction. Graphic Abstract