The Ni-B/SiO2 amorphous catalyst was prepared by KBH4 reduction at room temperature. The activities of the as-prepared catalysts with various Ni loading amounts were measured during the selective hydrogenation of acrylonitrile to propionitrile and compared with those of the corresponding Ni/SiO2 catalysts obtained by H-2 reduction at 773 K. For the Ni-B/SiO2 amorphous catalyst, its activity per weight Ni (R-H) first increased and then decreased with the increase of Ni loading. The maximum activity was obtained at 6.4 wt.% Ni. However, the R-H of Ni/SiO2 remained at the highest value up to 5.0 wt.% Ni. Then, it decreased gradually with the further increase of Ni loading. For the same kind of catalyst (Ni-B/SiO2 or Ni/SiO2), the TOF values remained almost constant irrespective of Ni loading, showing that their activity was mainly dependent on the metal surface area (S-Ni) The S-Ni of Ni/SiO2 catalyst is simply affected by the surface dispersion (mean particle size) due to its perfect reduction degree. However, the S-Ni of Ni-B/SiO2 catalyst was affected by both the surface dispersion and the reduction degree since the reducing ability of KBH4 is relatively poor. With the increase of Ni loading, the SNi first increased owing to the increase of reduction degree and then decreased due to the gathering of Ni particles at high Ni loading, which could account for the change of the RH With Ni loading. If one compares between the two kinds of catalysts, the higher TOF value of the Ni-B/SiO2 indicates that it was more active than Ni/SiO2 this may be attributed to the modification of the nature of Ni active sites by the alloying B. Both the structural effect and electronic effect have been discussed based on various characterizations.