The catalysts based on MoO3/Al2O3 were synthesized and tested using aqueous hydrogen peroxide as the oxidant in the oxidative desulfurization of thiophene, benzothiophene (BT) and dibenzothiophene (DBT) into the corresponding sulfones. Among catalysts tested, 15%(MoO3–WO3)/Al2O3 prepared by a conventional impregnation method was considerably active for the oxidation of thiophene, BT and DBT, which could achieve higher than 99.2% conversions at lower reaction temperature (≤338 K). The use of hexadecyltrimethyl ammonium bromide as the phase-transfer reagent in small amounts could promote the reaction efficiently.