The Catalytic oxidative desulfurization (Cat-ODS) comprises of molybdenum based catalyst, tert-butyl hydroperoxide (TBHP) as oxidant and dimethylformamide (DMF) as solvent for extraction. A series of polymolybdates supported alumina were prepared using the wet impregnation method. This potential catalyst was characterized by FTIR, FESEM-EDX and XPS for its physical properties. From catalytic testing, Fe/MoO3-Al2O3 calcined at 500°C was revealed as the most potential catalyst which gave the highest sulfur removal under mild condition .The sulfur content in commercial diesel was successfully reduced from 440 ppmw to 88 ppmw under mild condition followed by solvent extraction. Response surface methodology involving Box-Behnken was employed to evaluate and optimize Fe/MoO3/Al2O3 preparation parameters (calcination temperature, catalyst loading, and Fe loading) and their optimum values were found to be 550 ºC, 10 g/L, and 10%. of calcination temperature, catalyst loading, and Fe loading. Based on these results, the reaction mechanisms of peroxy oxygen were proposed.