Two kinds of mesoporous HPW/SiO2 composites, which have been synthesized respectively by the amino-functionalized (AF) method and evaporation-induced self-assembly (EISA) method, have been used as catalysts in the oxidative desulfurization process of dibenzothiophene(DBT). The catalytic performance results show that the catalyst synthesized by EISA method holds higher catalytic activity than that synthesized by the AF method. The difference of catalytic activity can be attributed to the different synthesis mechanism of two kinds of composites. In the AF method, the bonding force between HPW and SiO2 is strong acid-base interaction, which damages the Keggin structure. Whereas in the EISA process, electrostatic force and hydrogen bonds between W=O groups and Si-OH groups are main bonding forces. The hydrogen bond holds the electron-withdrawing effect, which increases the activity of nonbonding W=O groups in HPW and then results in the enhancement of the catalytic activity.