Site selective cross dehydrogenative aminations from precursors without preactivated C–H and N–H bonds have been challenging. Herein, a copper-catalyzed C2-site selective amination of p-aminophenol derivatives with arylamines has been developed. This approach precludes both partners from prefunctionalization and yields single site selective aminated products. This reaction proceeds smoothly with air as a terminal oxidant to produce the corresponding C2-site functional aminophenol derivatives in moderate to good yields.