Abstract: WP/γ-Al2O3 catalyst whios active component is tungsten phosphide was prepared by mechanical mixing, co-impregnation and stepwise-impregnation methods, respectively from the tungsten phosphate precursor by means of temperature-programmed reduction in highly-pure flowing hydrogen. The HDS activity of thiophene over these catalysts was examined. The result revealed that the methods used for catalyst preparation had some effect on the catalyst structure and activity to HDS of thiophent especially for the lower temperature reaction. With mechanical mixing method, the HDS activity of the catalyst prepared by mixing then reduction is higher than that prepared by reduction then mixing. With co-impregnation and stepwise-impregnation methods, the HDS activity of the catalyst prepared by calcination is higher than that without calcination or close to each other, respectively. Catalysts prepared by impregnation had higher HDS activity than that prepared by mechanical mixing.