A transition-metal-free approach was disclosed for intermolecular aryl C–N bonds formation between phenols and cyclic anilines via cross-dehydrogenative coupling (CDC) amination that was mediated by visible light, wherein K2S2O8 served as an external oxidant. The salient features of this protocol include circumventing the requirement for prefunctionalized starting materials and achieving single regioselectivity of amination adducts at room temperature.