Pyridinium bromochromate has been found to be a highly efficient and selective reagent for theα-monobromination of 1,3-diketones andβ-keto-esters in the absence of base,Lewis acid,or other catalyst.The products were formed in high to excellent yields under mild reaction conditions and in short reaction times. Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3-diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The products were formed in high to excellent yield. under mild reaction conditions and in short reaction times.