A series of Mo-KIT-6 catalysts were developed to photocatalytic oxidize sulfur compounds and promote effective product separation in a photocatalytic extraction oxidative desulfurization (PEODS) system with visible light, extractant [Omim]PF6 and oxidant H2O2. Morphological and pore structure characterization showed that Mo-KIT-6 possessed significant three-dimensional mesoporous structure and large specific surface area which enhanced mass transfer effect and be provided good dispersion of active sites. Doping of Mo enhanced the light absorption and promoted the photogenerated electron hole pair separation, resulting the improvement of the ability of photocatalytic oxidation desulfurization. Among the catalysts, the 15 wt% Mo doping KIT-6 revealed the best desulfurization performance and reached 100 % sulfur removal in 25 min. The circulation experiment proved that the good circulation performance and stability of the photocatalyst within 5 cycles. Radical scavenger experiments and ESR analysis confirmed that OH and h+ played a major role in the reaction. Furthermore, a possible photocatalytic desulfurization mechanism was proposed.