The selective catalytic hydrogenation of naphthalene to high-value tetralin was systematically investigated. A series of Al2O3 catalysts containing different active metals (Co, Mo, Ni, W) were prepared by incipient wetness impregnation. The effects of different active metals forms (oxidation, reduction, sulfuration) and reaction conditions on naphthalene hydrogenation were investigated and the catalysts were characterized by XRD, XPS, BET, NH3 TPD and SEM. Especially, Ni-Mo/Al2O3 was first used in this reactive system. The results show that the oxidative 4%NiO-20%MoO3/Al2O3 is the best catalyst for the preparation of tetralin. The conversion of naphthalene and the selectivity of tetralin can reach 95.62% and 99.75% respectively at 200 degrees C, 8 h and 6 MPa. Compared with reduced and sulfureted 4%NiO-20%MoO3/Al2O3 catalysts, oxidative 4%NiO-20%MoO3/Al2O3 has a well dispersed and uniform monolayer of the active metals, larger pore volume and size, and larger total acidity. NiO-MoO3/Al2O3 has a synergistic effect between NiO activity and MoO3 selectivity. (C) 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.