Abstract A highly efficient palladium (II)-catalyzed hydration of a wide range of alkynylphosphonates to the corresponding β-ketophosphonates has been developed to give high yields at 80 C in 1, 4-dioxane, with no acidic or alkaline cocatalysts required. The described catalytic system should provide an efficient alternative to highly toxic mercury- catalyzed methodologies and be useful in synthetic programs.