Abstract: Ni-MgO/Al2O3 catalysts for hydrogenation of adiponitrile to hexamethylenediamine were prepared by impregnation method and the prepared catalysts were characterized by BET, XRD and H2-TPR techniques. The effect of various MgO contents on catalyst activities was studied. Results indicated that the formation of MgO-NiO solid solution in Ni-MgO/Al2O3 catalysts increased the number of alkaline active sites which could effectively inhibit the side reaction of deamination. The effect of reaction conditions on the yield and selectivity of hexamethylenediamine was investigated base on single factor experiments. The optimal reaction conditions were determined as follows: using catalyst with MgO mass content of 6% and a dosage of 5% (based on total mass of raw materials), adopting ethanol as solvent, a reaction temperature of 70℃, a hydrogen partial pressure of 1.5 MPa, ethanol/adiponitrile mass ratio of 2.0 and with a stirring speed of 1 000 r/min. Under such optimal conditions, the conversion of adiponitrile and the selectivity of hexamethylenediamine reached 99.9 % and over 98.4%, respectively.