A meaningful copper-catalyzed chemo-selective oxidative alkylamination of maleimides with secondary alkyl amines and simple alkanes has been developed. This transformation exhibits excellent compatibility with an array of polyfunctionalized organic amines and inactivated alkanes, modular synthesis of 3-carbo-4-amino maleimides under simple, and efficient catalytic systems.Detailed mechanistic studies support the formation of 3-amino maleimides and alkyl radical intermediates and their subsequent radical alkylation in the reaction process.