A skeletal Ni-P amorphous alloy catalyst (referred to Raney Ni-P) was prepared by alkali leaching an amorphous Ni-Al-P ahoy obtained by the rapid quenching technique. Its catalytic performance was measured during the selective hydrogenation of adiponitrile (ADN) in gas-solid phase at 1 atm pressure, 473 K, and in the absence of ammonia. The as-prepared catalyst exhibited higher activity and better selectivity toward 1,6-hexanediamine (HMA) than other Ni-based catalysts, such as the crystalline Raney Ni-P, regular Ni-P amorphous alloy catalyst, Raney Ni, and Ni/Al2O3. According to various characterizations, such as BET, H-2 chemisorption, X-ray diffraction (XRD), extended X-ray absorption fine structure measurements (EXAFS), X-ray photoelectron spectroscopy (XPS), and differential scanning calorimetry (DSC), the correlations of the structural characteristics and the surface electronic states to the catalytic behavior were discussed. (C) 2000 Elsevier Science B.V. All rights reserved.