Benzylic alcohols cross-couple directly with concentrated H(3)PO(2) using Pd/xantphos (1 or 2 mol-%). Depending on the substrate, DMF at 110°C, or t-AmOH at reflux with a Dean-Stark trap, can be used. A broad range of benzylic alcohols reacted successfully in moderate to good yields. The preparation of other organophosphorus compounds (phosphinic and phosphonic acids) is also demonstrated.Asymmetric reaction with (R)-1-(2-naphthyl)ethanol provided the corresponding H-phosphinic acid in 77% ee. The methodology provides a green, PCl(3)-free, entry into benzylic-H-phosphinic acids.