Photosensitized oxygenation has been recognised as a modern method of incorporating oxygen into a substrate, as it offers environmentally benign alternatives to several conventional synthetic procedures. A metal-free aerobic selective sulfoxidation photosensitized by a perylene diimide photocatalyst has been developed. The reaction utilizes visible light as the driving force and molecular oxygen as the oxidant. The advantages of the developed method include high efficiency and selectivity, extremely simple operation and work-up procedure, mild reaction conditions, and practical application in late-stage functionalization.