A series of POM-based hybrid materials: phosphotungstic acid supported ceria (HPW-CeO2) have been synthesized and characterized by X-ray diffraction (XRD), Thermogravimetric-differential scanning (TG-DSC) analysis, Scanning electron microscopy (SEM), FT-Raman, FT-IR, UV-vis, and BET analysis. Combined with [C(8)mim]BF4, the catalyst was very efficient on the removal of DBT by using H2O2 as the oxidant under mild reaction conditions, which could reach a sulfur removal of 99.4%. The amount of catalyst, O/S molar ratio, reaction time and temperatures were evaluated in detail, and the favorable operating condition was obtained as well as the kinetic study of substrates. The structure-activity relationship was systematically investigated. Oxidative desulfurization system could be recycled for ten times without significant decrease in activity. A mechanism was proposed to investigate the oxidation process of DBT. (C) 2013 Elsevier B.V. All rights reserved.