Mesoporous catalysts [HPMo][HTAC]2/SiO2 with different loading amount of [HPMo][HTAC]2 were prepared by sol–gel method. The catalysts were characterized by XRD, FT-IR, SEM and pore structure parameters. The catalytic activity for the oxidative desulfurization of benzothiophene (BT) and dibenzothiophene (DBT) was evaluated using hydrogen peroxide as an oxidant. Results of the charaterization show that the Keggin structures of all the loaded catalysts were kept and [HPMo][HTAC]2 was highly dispersed on the surface of SiO2. The desulfurization rate of the catalyst 20%[HPMo][HTAC]2/SiO2 can be up to 91% for DBT and 75% for BT in 2 h.