A wide range of benzyl carbonates reacted with dimethyl phosphonate or diphenylphosphine oxide in the presence of the palladium catalyst, [Pd(eta(3)-allyl)Cl](2)-DPEphos, to give dimethyl benzylphosphonates and benzyldiphenylphosphine oxides in high yields. The catalytic phosphonylation was applied to the one-pot synthesis of alkenes from the benzyl esters.