A fast, mild, and highly efficient method for the intermolecular coupling of 1, 3-dicarbonyl compounds using cerium ammonium nitrate in CH3CN/CH3OH/H2O has been described. The procedure provided a convenient method for the synthesis of 1, 4-diketone derivatives with excellent yields (up to 96%) and powerful evidence for the oxidation mechanism mediated by cerium ammonium nitrate.