A class of chiral Rh(I) catalysts containing monodentate phosphorous acid diesters tautomerized from the corresponding secondary phosphine oxides was discovered by serendipitous hydrolysis of phosphoramidite ligands. The evolved catalysts demonstrated unprecedented enantioselectivities (98-99% cc) and high catalytic activities (as low as 0.01 mol% catalyst loading) in asymmetric hydrogenations of a wide variety of alpha-aryl-/alkyl-substituted ethenylphosphonic acids, providing a facile approach to the corresponding enantiopure phosphonic acids with significant biological importance.