The Ni-B/SiO2 amorphous catalyst was prepared by impregnation of silica support with NiCl2 aqueous solution following the chemical reduction with KBH4. The influence of calcination and pretreatment temperature on its activity was investigated by using acrylonitrile hydrogenation as a probe. On the one hand, it was found that the activity of the Ni-B/SiO2 amorphous catalyst first increased and then decreased when the precursor (Ni2+/SiO2) was calcined at the temperature from 273 to 773 K in Ar flow. The optimum calcination temperature was then determined as 473 K. On the other hand, when the as-prepared Ni-B/SiO2 amorphous catalyst was pretreated at the temperature from 273 to 873 K in Ar flow, the activity of the catalyst first remained almost unchanged up to 573 K and then decreased abruptly with the further increase of temperature. According to various characterizations, such as inductively coupled plasma (ICP), differential scanning calorimetry (DSC), X-ray photoelectron spectra (XPS), X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS), it was concluded that the effect of the calcination temperature on the activity should mainly be attributed to the surface density of metallic nickel; while the effect of the pretreatment temperature on the activity was caused by the transformation from amorphous structure to crystalline structure.