In this paper, the performance of catalytic oxidative desulfurization (ODS) was studied using catalyst MoO3/4A which was prepared by depositing molybdenum on 4A molecular sieve, a microporous material. Dibenzothiophene (DBT) and benzothiophene (BT) were selected as the target compounds, and oil-soluble cyclohexanone peroxide (CYHPO) as an oxidant. The effects of relevant parameters on ODS including molybdenum loading, reaction temperature, reaction time, the molar ratio of CYHPO/DBT and the weight of catalyst MoO3/4A were investigated, and the oxidation mechanisms as well as the kinetics were also examined individually. The catalytic oxidative removal of DBT and the residual sulfur content reached 99.0% and 5 ppmw, respectively, at an optimal catalytic condition of Mo loading of 6 wt. %, molar ratio of CYHPO/DBT of 2.5 and volume mass ratio of model gasoline to catalyst MoO3/4A of 100 at 373 K over 30 min. The optimal design of experiments using Box-Behnken method was employed to evaluate the effects of individual process variables such as, reaction temperature, reaction time and molar ratio of CYHPO/DBT and their optimum values were found to be 340 K, 38 min and 3.8, respectively, to achieve a conversion of 100%. The catalyst could be reused for 4 times before the total DBT content of treated model gasoline was higher than 10 ppmw, and the activity of the desulfurizatioh system was above 95% after regenerating for 9 times. The catalytic oxidation of DBT and BT fitted the pseudo-first order kinetic model pretty well. The catalyst MoO3/4A was characterized by the scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectrum (XPS), and the data showed that a thin layer of active components was covered on the catalyst surface which helped to explain the satisfactory catalytic performance. (C) 2016 Elsevier B.V. All rights reserved.