The solar-driven selective oxidation of amines to imines has attracted widespread attention due to its green and non-polluting nature, as well as its high selectivity. In this study, a unique S-scheme BiOCl/UiO-66(Ce/Ti) heterojunction was ?rst constructed as an organic aerobic photocatalyst. Under visible light irradiation with water as the sole solvent, the yield of the imine reached 98%. The S-scheme charge transfer mechanism was veri?ed through in situ X-ray photoelectron spectroscopy and electron paramagnetic resonance measurements, revealing the source of excellent photocatalytic activity. Additionally, the synergistic e?ect of the interface microenvironment generated by the interaction between OVs and Ce–Ti was found to play a signi?cant role in the photocatalytic oxidation process. This work emphasizes the importance of designing a heterojunction interface microenvironment (IME) for achieving e?cient photocatalytic selective oxidation of amines.