In this work, a simultaneous photocatalytic extraction-oxidation system for desulfurization of a model fuel has been investigated. To do this, S-doped TiO2 and S-doped TiO2/BiVO4 photocatalysts were synthesized via sol-gel and hydrothermal methods. Different analyses such as FT-IR, Raman, DRS, XRD, FE-SEM, TEM, BET, EDS, and XPS were used to characterize catalysts. According to the results, the S-doped TiO2/BiVO4 catalyst showed the highest photocatalytic activity for the removal of dibenzothiophene from the model fuel. The reaction was investigated under different conditions such as the catalyst amount, temperature, time, oxidizing value, extracting solvent, and the fuel type. Under optimal conditions, 89.3 % removal of dibenzothiophene was obtained. The catalyst can be recovered up to 3 times without significant reduction in catalytic activity. To evaluate the effect of the TiO2/BiVO4 heterojunction on its photocatalytic activity, DFT calculations were conducted. The obtained results confirmed the greater efficiency of the synthesized composite.