A series of ultrafine Ni-P-B amorphous alloy catalysts were prepared by a chemical reduction method under various conditions. Two different nickel salts (nickel chloride and nickel acetate) and two solvents systems (water and ethanol in water) were used in preparation. The catalysts were characterized with elemental analysis, XRD, nitrogen sorption, TEM, and XPS. Liquid phase hydrogenation of furfural was used to compare the hydrogenation capabilities of these catalysts. The different preparation conditions significantly influence morphology, particle size, and surface area of the catalyst, subsequently affecting the hydrogenation properties. The catalyst prepared with aqueous ethanol solvent has a flossy morphology and results in higher surface area and higher activity of the catalyst. The type of nickel salt did not show significant influence on the properties of the catalyst. Different preparation conditions did not influence the electronic state of nickel.