In this work, an experimental study was carried out to obtain the reactivity of different organic sulfur compounds and to examine the effect of various parameters, such as temperature, solvent and the amount of oxidant reagent in oxidative desulfurization (ODS) reaction. The oxidation was performed through a vanadium based catalyst in the presence of hydrogen peroxide under mild reaction conditions, atmospheric pressure and temperature range of 303-343 K. The sulfur compounds studied were: 2-methylthiophene (2-MT), 2,5-dimethylthiophene (2,5-DMT), benzothiophene (BT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). All of them are typical thiophenic sulfur compounds present in diesel fuels. A synthetic diesel was prepared with these compounds in hexadecane. The experimental results showed that oxidation reactivities decreased according to the following order: DBT > BT > 4-MDBT > 2-MT > 2,5-DMT > 4,6-DMDBT. A fraction of the S compounds removed from the diesel phase, was not transformed to its corresponding sulfone, under these experimental conditions. It is only removed as sulfur compound by extraction, without ODS reaction. The surplus amount of oxidant promoted the equilibrium reaction, but the thermal decomposition of oxidant and oxidation reactions produces water, which inhibits the ODS reactions. Therefore, the controlled addition of H2O2 improves ODS reactivity of sulfur compounds. (c) 2005 Elsevier B.V. All rights reserved.