Vanadium-based ultra-stable Y zeolite loaded with phosphotungstic acid (V-HUSY/HPW) was prepared by the demetalation-metalation method using H-type ultra-stable Y zeolite (HUSY) as the support, and ammonium metavanadate and phosphotungstic acid hydrate (HPW) as raw materials. The structure, morphology, and elemental content were studied by XRD, FTIR, UV-vis, TEM, SEM, N2 adsorption-desorption and ICP-OES. The V-HUSY/HPW was employed in the oxidative desulfurization reaction of dibenzothiophene (DBT) model oil to investigate the effects of V and HPW additions on the desulfurization rate and to test the cycling stability of the catalysts and speculate on the mechanism of the oxidative desulfurization reaction. The results showed that V species were introduced into the framework of the HUSY by the demetalation-metalation method, while HPW was loaded on the surface of HUSY by the impregnation method. V-HUSY0.1/HPW0.5 prepared at the additions of V and HPW of 0.1 mmol and 0.5% (in percent by mass of V-HUSY), respectively, had the best performance. The desulfurization rate of the model oil was 99.5% at a reaction temperature of 60 ℃ and a reaction time of 20 min under the conditions of 0.1 g of V-HUSY0.1/HPW0.5, 20 mL of DBT model oil (DBT mass concentration of 360 mg/L), and 15.8 μL of tert-butyl hydroperoxide (TBHP) as oxidant. After 6 cycles, the desulfurization rate of DBT model oil was still up to 98.3%. During the oxidative desulfurization process, the hydroxyl radical (?OH) was the main active species, which could convert DBT into more polar sulfone and then retained in the pore structure of the catalyst, so that a one-step in-depth desulfurization could be achieved without the need of extraction.