The oxidative desulfurization of thiophene in a synthetic mixture of thiophene and iso-octane was investigated with copper loaded titanium silicate-1 (TS-1) catalyst in presence of hydrogen peroxide as oxidising agent and the conversion was enhanced by 22% at 240 min on addition of 1.05 wt.% copper in TS-1. The optimal design of experiments using box-behnken method was employed to evaluate the effects of individual process variables such as, reaction temperature, amount of catalyst and moles of hydrogen peroxide per mole of thiophene and their optimum values were found to be 70 degrees C, 0.45 g (22.5 mol/L of iso-octane) and 19.9 mol (in 20 ml of iso-octane), respectively, to achieve a conversion of 93%. The influence of mass transfer effects on the desulfurization reaction was minimized by selecting proper degree of agitation and catalyst size. An empirical kinetic model was used to interpret the rate data. The apparent activation energy was found to be 28.67 kJ/mol. (C) 2010 Elsevier Ltd. All rights reserved.