In order to obtain the clean fuel, two types of inorganic–organic hybrid catalysts with core–shell structureshave been prepared as efficient and reusable catalysts for oxidative desulfurization, in which ionicliquids (1-vinylimidazole and 4-vinylpyridine) were grafted and polymerized on the surface of siliconthrough free radical polymerization and polyoxometalates (H3PMo6W6O40, attributed as PMoW) wasfunctionalized on the surface of silicon. The as-prepared catalysts were characterized by FT-IR, UV–Vis,N2 adsorption–desorption, SEM and TEM. It could be proved that these two types of catalysts show highsulfur removal efficiency over 98% in the model fuel with 2000 ppm of DBT under mild reaction condition. The effective catalytic abilities of synthesized catalysts are mainly attributed to the hierarchical functionalcore–shell structures. The successful preparation of the PILs-polyoxometalates based catalysts withhigh catalytic activities could provide the demonstration of the application of polymer in oxidativedesulfurization.