Mesoporous molecular sieve SBA-15-W was synthesized using ethyl orthosilicate (TEOS) as raw material and bacillus (W) as auxiliary template. And then TiO2 supported photocatalytic oxidation desulfurization catalyst TiO2-SBA-15-W was obtained. The samples were characterized by XRD, N2 adsorption-desorption, SEM, EDS, FTIR, XPS, UV-Vis and PL. The results showed that the addition of bacillus made the mesoporous order degree and pore diameter of TiO2-SBA-15 increase, the ability of the catalyst to absorb ultraviolet light enhance and the photoelectron-hole compound rate decrease. Dibenzothiophene (DBT) was used as a probe to evaluate the catalytic performance of the catalyst. The results indicated that the photocatalyst TiO2-SBA-15-W with 1% bacillus content (based on the mass of SiO2, the same below) had better catalytic performance. Under the optimum reaction condition of catalyst dosage of 1% (based on the mass of the model fuel, the same below), n(O)∶n(S)=20∶1 in hydrogen peroxide/model fuel, V(extractant)∶V (model fuel) =1∶1, the desulfurization rate of the model fuel reached 90.6% under irradiation for 120 min, which was 11.8% higher than that of TiO2-SBA-15. The mechanism of photocatalytic oxidative desulfurization (PODS) was proposed. Superoxide radicals (•O2-) and holes (h+) were considered to be the main active species of PODS.