A copper-catalyzed direct C(sp2)−H bond aminosulfonylation of maleimides is demonstrated. This protocol enables concurrent construction of C(sp2)−N and C(sp2)−SO2 bonds in one-step and features high efficiency, broad substrate scopes, good functional-group tolerance, and mild reaction conditions. Preliminary mechanistic studies indicate that the reaction probably involves a radical way. Significantly, this method is applicable to synthesize derivatives of pharmaceuticals such as Desloratadine, Fluoxetine, Atomoxetine, and Maprotiline.