Dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene are typical thiophenic sulfur compounds that exist in diesel fuels. Using toluene solutions of the model compounds, experiments were carried out to compare the reactivity of the different dibenzothiophenes in oxidation reactions, a key step for oxidative desulfurizations. A series of polyoxometalate/H2O2 systems were evaluated for dibenzothiophene oxidation. The H2O2 solutions of phosphotungstic acid and its salt were very active catalyst systems for the model compound oxidation, while their molybdenum counterpart systems were much less active. The H2O2 solutions of silicotungstic and silicomolybdic compounds were the least active catalyst systems for the reaction. Oxidation reactivities decreased in the order of dibenzothiophene > 4-methyldibenzothiophene > 4,6-dimethyldibenzothiophene, the same reactivity trend that exists in HDS. However, the oxidation of the dibenzothiophenes was achieved under mild reaction conditions and it was easy to increase reaction temperature or reaction time to achieve high oxidation conversions, even for the least reactive 4,6-dimethyldibenzothiophene. Apparent activation energies of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene oxidation were 53.8, 56.0, and 58.7 kJ/mol, respectively. These activation energies indicated a decrease in reactivity of dibenzothiophenes as methyl substitutes increased at the 4 and 6 positions on dibenzothiophene rings. Interestingly, in a formic acid/H2O2 system, the oxidation reactivity of the dibenzothiophenes showed the reverse trend, suggesting that steric hindrance might play a role when bulky polyoxoperoxo species, which likely form in a hydrogen peroxide solution, act as catalysts. Crown Copyright