A series of Ni-B/SiO2 amorphous catalysts were prepared by chemical reduction; these were employed in the liquid phase selective hydrogenation of stearonitrile. In comparison with other Ni-based catalysts, such as the corresponding crystallized Ni-B/SiO2, the Ni/SiO2 obtained by hydrogen reduction at 673 K, and even the commercially available Raney Ni, the as-prepared Ni-B/SiO2 amorphous catalyst exhibited higher activity and better selectivity to primary amine; this can mainly be attributed to the promoting effect of its amorphous structure and to alloying B. With the increase of Ni loading, both the activity and the selectivity increased. It was also found that NH3 additive in the reaction media was favorable for the production of primary amine, though the reaction activity was slightly inhibited. However, no significant promoting effect of KNO3 doped SiO2 was observed. Such results were discussed based on various characterizations, including BET, XPS, XRD, ICP, SEM, and NH3-TPD.