A novel and selective method for the simple copper-catalyzed α-amination of α-aminocarbonyl compounds to afford 2-amino-2-iminocarbonyl and 2-amino-2-oxocarbonyl compounds is reported. This transformation is achieved by C(sp3)−H and N−H bond oxidative cross-coupling and selective C−N bond oxidative cleavage. This reaction system has a broad reaction scope, providing a facile pathway for the α-functionalization of α-amino ketones.