Mesoporous silica-zirconia supported phosphotungstic acid was synthesized by evaporation induced self-assembly method and used as oxidative desulfurization catalysts. The structural properties of as-prepared catalysts were characterized using various analytical techniques including X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption desorption. The experimental results showed that HPW was highly dispersed on mesoporous framework. The surface acidity of catalysts was analyzed by FTIR measurement of adsorbed pyridine.The surface Lewis acidity was improved with increasing the content of zirconium in the samples. The mesoporous composites were used as catalysts with H2O2 as oxidant for oxidative desulfurization of model fuel. The catalytic activity results showed that the surface Lewis acid sites acted as selective adsorption active sites for dibenzothiophene, which facilitated the sulfur removal from model fuel in the presence of arene. A slight decrease in activity of the recovered catalyst used in the proceeding rounds indicated the reusability of the catalyst.