A stable and isolable bis[(tetrabutylammonium) di-μ-iodo-diiododicuprate(I)] complex has been identified for the direct oxidative synthesis of α-ketoamides from substituted aryl methyl ketones and secondary amines in the presence of molecular oxygen. Gratifyingly, this Cu(I) complex acts as an effective catalytic system with enhanced solubility in both water and organic solvents. These reactions were effectively accelerated by microwave irradiation in water and were applied for the synthesis of a variety of substituted α-ketoamides with good yields. It was interesting to note that, in these optimized microwave reaction times, α-ketoamides were the exclusive products and amide byproducts observed in previous reports were not formed.