In this study, an efficient extraction-oxidation catalytic system for deep desulfurization of a model fuel was explored. For this propose, a series of vanadium phosphate catalysts supported on mesoporous silica material (KIT 6) were prepared by the sol–gel method. Structural and textural characterization of the catalysts were performed by various techniques including SEM, TEM, ICP-EOS, FT-IR, N 2 adsorption, XRD. It was found that the catalyst with maximum vanadium phosphate loading (VPK-C) show the best catalytic activity in dibenzothiophen removal based on oxidative desulfurization (ODS) process. The different reaction conditions such as temperature and mole ratio of H2O2 were investigated in the catalytic system. Moreover, the effect of solvent by using different extarctants is studied. Under optimum conditions, the DBT removal rate reached up to 97%. In addition, the effect of aromatic compounds on catalytic activity was evaluated and it was observed that catalytic activity is slightly affected. The catalyst could be recycled 5 times without significant decrease of catalytic activity.