MgO-Al2O3 support was synthesed by precipitation method in the presence of different surfactants. Series of Mo/MgO-Al2O3 catalysts were prepared by ultrasonic assisted incipient-wetness impregnation method with molybdenum as the active component. All the samples were characterized by N2 adsorption, X-ray diffraction, H2 temperature-programmed reduction, atomic emission spectrometry, and Raman spectroscopy. The catalytic activity of catalysts for COS hydrogenation in simulated coke oven gas was evaluated on a fixed-bed equipment. The results indicate that the structure of MgO-Al2O3 support could be modified by using surfactants during its preparation process. Polyoxyethylene-polyoxypropylene-polyoxyethylene(P123) could increase the average pore diameter and promote the exposure of(440) crystal plane of Mg2AlO4 in support, which would promote the formation of octahedral coordination molybdenum species in the Mo/MgO-Al2O3 catalyst and generate more MoS2 active sites in pre-sulfurization treatment process. With the adding of ethylene glycol(PEG) or hexadecyl trimethyl ammonium bromide(CTAB), the pore size distribution of catalyst support could be mainly controlled in the range of 2-5 nm, while the expesure of(511) crystal plane of Mg2AlO4 in the catalyst support could be promoted, which would enhance the interaction between molybdenum and support, and thus reduce the activity and stability of Mo/PEG-MgO-Al2O3 and Mo/CTAB-MgO-Al2O3 catalysts. Mo/P123-MgO-Al2O3 has the highest activity towards COS hydrogenation, and its conversion rate for COS reaches 87.3%.