The catalytic hydrogenations of sulfolene to sulfolane over different supported amorphous Ni-B alloy catalysts and Raney nickel catalysts were performed in a batch reactor under pressurized conditions. The deposition of amorphous Ni-B particles (average Ni-B particle size = 40.5 nm) on MgO was carried out by a silver-catalyzed electroless plating technique. The influence of significant variables such as the plating temperature and content of potassium borohydride, was investigated in the preparation. The silver and Ni-B loadings in the catalyst were varied as well. The catalysts were characterized by X-ray powder diffraction (XRD), inductively coupled plasma (ICP) spectrometry, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), and N-2 physisorption. The load of nickel on MgO increases with the plating temperature, use of potassium borohydride, and loading of silver. The best Ni-B/MgO catalyst showed a remarkably superior catalytic activity to that of the Ni-B/TiO2 or Raney nickel catalyst, and the difference is ascribed to the nature of amorphous structure and the characteristics of amorphous Ni-B particles on MgO.