Attaching π‐conjugated molecules onto TiO2 can form surface complexes that could capture visible light. However, to make these TiO2 surface complexes durable, integrating 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) or its analogues as a redox mediator with photocatalysis is the key to constructing selective chemical transformations. Herein, sodium 6,7‐dihydroxynaphthalene‐2‐sulfonate (DHNS) was obtained by extending the π‐conjugated system of catechol by adding a benzene ring and a substituent sodium sulfonate (−SO3−Na+). The DHNS−TiO2 showed the best photocatalytic activity towards the blue light‐induced selective aerobic oxidation of benzylamine. Compared to TEMPO, 4‐amino‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (4‐amino‐TEMPO) could rise above 70% in conversion of benzylamine over the DHNS−TiO2 photocatalyst. Eventually, a wide range of amines could be selectively oxidized into imines with atmospheric O2 by cooperative photocatalysis of DHNS−TiO2 with 4‐amino‐TEMPO. Notably, superoxide (O2•−) is crucial in coupling the photocatalytic cycle of DHNS−TiO2 and the redox cycle of 4‐amino‐TEMPO. This work underscores the design of surface ligands for semiconductors and the selection of a redox mediator in visible light photocatalysis for selective chemical transformations.