Abstract: The XO-Fe2O3/γ-Al2O3 (X: La, Ce, Co and Cu) catalysts in Fenton system (catalyst + oxidant H2O2) were prepared and characterized by XRD, SEM and BET techniques. The oxidation removal of thiophene in model gasoline (n-octane solution) with heterogeneous Fenton system was tested to investigate the effect of kind of metals, n(H2O2)/n(S) and catalyst dosage. The characterized results demonstrate that the catalysts have meso-pore structures. The desulfurization tests indicate that the catalyst Fe2O3/γ-Al2O3 promotes the production of ?OH radical from H2O2 to oxidize the thiophene, thus improves the removal of thiophene. The addition of second metal can improve the catalytic activity of Fe2O3/γ-Al2O3. Among of them, Cu is the best one. Under the conditions of temperature 333K, catalyst dosage 0.2g, n(H2O2)/n(S)=7.40 and reaction time 120 min, 95.3% of thiophene can be removed. The S content in product is reduced to 9.4μg/g, which meet the ultra-deep desulfurization object.