A series of NiB(P) and NiCoB amorphous alloys were prepared by chemical reduction. Their catalytic activities in hydrogenation of sulfolene were evaluated in a 250 ml stainless autoclave. Influences of solvent and preparation temperature on the catalytic activity of NiB amorphous alloy were studied. Effects of reaction temperature and stirring rate on the catalytic properties of NiB amorphous alloy were researched; Raney Ni properties were also studied. The relationship between particle size of NiB, NiP and NiPB amorphous alloys and their catalytic behaviors has been discussed according to SEM, TEM and ICP results. Comparing the activities of NiCoB amorphous alloys with NiB, CoB and Raney Ni catalysts, we found that, NiCoB amorphous alloys with mole ratio of Ni/Co at 2.4 have much higher activity in hydrogenation of sulfolene.