Three-dimensionally ordered (3DOM) macroporous phosphotungstic acid/SiO2 (HPW/SiO2) materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization (ODS) of the model fuel oil. The obtained HPW/SiO2 materials were characterized through scanning electron microscopy, powder X-ray diffraction, N2 sorption, and Fourier transform infrared spectroscopy. The results indicated that 3 DOM HPW/SiO2 possessed hierarchical pore architectures which contained ordered macropores and disordered mesopores, with the Keggin type HPW embedded in the framework of pore structure. The removal rate of dibenzothiophene (DBT) could reach 100％ under the optimum conditions, moreover. The performance was only slightly decreased for the regenerated catalyst after 7 cycles.