A novel vanadium-catalyzed one pot domino reaction of 1,2-diketones with amidines has been identified that enables their transformation into imides and amides. The reaction proceeds by dual acylation of amidines via oxidative C(CO)-C(CO) bond cleavage of 1,2-diketones to afford N,N'-diaroyl-N-arylbenzamidine intermediates. In the reaction, these intermediates are easily hydrolyzed into imides and amides through vanadium catalysis. This method provides a practical, simple and mild synthetic approach to access a variety of imides as well as amides in high yields. Moreover, one step construction of imide and amide bond with long chain alkyl group is an attractive feature of this protocol.