A series of bulk and supported NiB amorphous alloy catalysts with different particle sizes were prepared by different chemical reduction methods. By adding a certain volume of NH3 to the reaction system and adjusting the reaction temperature, respectively, the velocity of the reaction between Ni2+ and BH4 - could be controlled and the NiB alloys with particle sizes ranging from 10 to 400nm were obtained. A novel method to prepare the supported NiB catalyst, the powder electroless plating method was also studied. The bulk and supported NiB catalysts were characterized by XRD, ICP and TEM. Hydrogenation of sulfolene was selected as the probe reaction to investigate their catalytic performance. The results revealed that the NiB/MgO prepared by Ag inducing electroless plating showed much higher catalytic activity than Raney Ni catalyst, and the powder electroless plating was a promising method to prepare the supported NiB amorphous alloy catalysts.