Quaternary Ni-Co-W-B amorphous alloys were prepared by chemical reduction of the aqueous solution of nickel and cobalt salts and sodium tungstate with potassium borohydride. The catalytic activities of the as-prepared materials were measured through liquid phase hydrogenation of benzene under moderate pressure. In comparison with Ni-Co-B, the as-prepared Ni-Co-W-B amorphous alloys showed superior activity, attributable to the promoting effect of tungsten on the microstructure of the alloys as revealed by XPS, XRD and DSC measurements.