In order to reduce the emission of SOx in the environment, sulfur compounds must be removed efficiently from fuels. Three-dimensional highly ordered meso-macroporous HPW/TiO2 (3DO m/M HPW/TiO2) materials were synthesized successfully by sol-gel method and applied as oxidative desulfurization catalyst for the model fuel. The characterization results displayed the existence of highly ordered meso-macroporous structures and the Keggin type of HPW was highly dispersed in TiO2 framework. The effect of catalyst on desulfurization under different reaction conditions was studied systematically. The results showed that the catalyst exhibited excellent desulfurization performance in the hydrogen peroxide oxidation system, which could be explained by the unique meso-macroporous structure of catalyst. In addition, the catalyst showed good cycling performance and the removal rate of DBT still reached 96.1％ even after 6 cycles, providing a feasible method for the development and application of fuel deep desulfurization catalysts.