The effective and highly selective aerobic oxidation of sulfides to sulfoxides under green and mild conditions is still an important but challenging process. Here we present a photocatalytic system for sulfide oxidation to sulfoxides with high yields under blue LED irradiation. The photo-oxidation was carried out in water with oxygen over a bismuth-rich catalyst of Bi₄O₅Br₂. The apparent quantum efficiency of sulfide oxidation reached 57.4%. The developed system provided a simple, robust, green and sustainable promising candidate for the practical application of sulfide oxidation.