The supported NiB amorphous alloy catalysts were prepared by the chemical reduction method. Crystalline structures, thermal stability、adsorption property of α-pinene、surface area and acid properties of the catalysts were characterized by XRD,DSC, in-suit FTIR, BET and TPD. The α-pinene hydrogenation reaction was chosen to investigate the catalytic properties and selectivity of the catalysts.The results indicated that α-pinene formed chemical adsorption under synergistic action of NiB amorphous alloy catalysts and supports acid site, acid strength affected catalyst’s selectivity,the percent conversion of pinene is 89.6% by using the supported NiB/ZrO2-Al2O3 amorphous alloy catalysts,the catalyst’s selectivity is 91.2%.After 70h reaction, the percent conversion of pinene reduced by 10% while the catalyst’s selectivity remain virtually unchanged.