A series of ultrafine Ni-Px-Bv amorphous alloy catalysts with various atomic ratios were prepared by a chemical reduction method. The catalysts were characterized with respect to elemental analysis, XRD, nitrogen sorption, DSC, SEM, TEM and XPS. Hydrogenation of furfural was used to test the catalytic properties of the catalyst. The sample prepared in ethanol had a higher surface area and a higher activity. The specific activity per surface area of the catalyst is in the order: Ni74.5P12.1B13.4>Ni72.5 P2.0B25.5 ≅ Ni83.9P9.0B7.1> Ni85.0P15.0>>Ni71.4 B28.9> Raney nickel. The modified nickel catalysts by the different electron transference, boron donates electrons to nickel and phosphorus draws electrons from nickel, dramatically revealed a markedly different catalytic property. The ultrafine Ni-P-B amorphous alloy catalyst, combining the effects of metalloid elements and the features of ultrafine amorphous structure, can be a very effective catalyst for the liquid phase hydrogenation reaction than Raney nickel.