A supported SiW12O40-based ionic liquid (SiW-IL) catalyst with high catalytic activity is designed and synthesized by sol-gel method. The supported catalyst had amphiphilic property, making it exhibit good catalytic performance in solvent-free oxidative desulfurization system. The removal of dibenzothiophene (DBT) with the supported catalyst reached 99.9%, while the sulfur removal is only 6.3% with SiW-IL. The characterizations show that SiW-IL is supported on the carrier successfully and the supported catalyst had a sheet-shaped morphology. Then, various of experimental conditions were taken into consideration to investigate the influences of the desulfurization efficiency and the optimal conditions were obtained. Additionally, sulfur removal of different substrates decreased in the following orders: DBT > 4-MDBT > 4,6-DMDBT > BT under the same conditions. GC-MS analysis was employed to study the mechanism of the desulfurization, DBT sulfone was proved to, be the oxidizing product of DBT. Moreover, the supported catalyst had a good thermal and chemical stability, and sulfur removal of DBT still remained 96.2% after recycling 7 times. (C) 2015 Elsevier B.V. All rights reserved.