As strict regulations of fuel specifications implemented, oxidative desulfurization process (ODS) is considered as one of the promising technologies to achieve deep desulfurization under mild conditions. Herein, amphiphilic polyoxometalate-based supported silica [C(4)mim](3)PW12O40/SiO2 was successfully synthesized by a facile hydrothermal process and employed in ODS process. The composition and structure of obtained hybrid samples were characterized by means of FT-IR, XPS, Raman, P-31 MAS NMR, UV-vis, wide-angle XRD, N-2 adsorption desorption and SEM. The experimental results indicated that the as-synthesized materials maintained the integrity of architecture of polyoxometalate-based ionic liquids (POM-based ILs), which were finely dispersed into the silica matrix. Besides, the sample [C(4)mim](3)PW12O40/SiO2 possessed moderate hydrophilic hydrophobic balanced surface leading to higher sulfur removal. Moreover, the effects of the amount of catalyst, H2O2/DBT molar ratio, temperature, types of sulfur-containing substrate on the sulfur removal were also investigated in detail. Under optimal conditions, dibenzothiophene (DBT) could be completely removed in 30 min. (C) 2015 Elsevier B.V. All rights reserved.