Two kinds of ultrafine Co-B amorphous alloy catalysts, denoted as P-1 Co-B and P-2W Co-B, were prepared by chemical reduction with borohydride in aqueous or 50% (v/v) ethanol/water solution, respectively. In comparison with the corresponding Co-based crystalline catalysts and Ni-based catalysts, these catalysts exhibited higher activity during the liquid phase glucose hydrogenation, possibly due to the unique amorphous characteristics and the lower d-band electron density, which was favorable for hydrogen dissociative chemisorption. Addition of Cr-, Mo- or W-promoters could further increase the conversion of Co-B amorphous catalyst, which was mainly attributed to the dispersion effect of promoters and the adsorption and polarization of carbonyl groups by these promoters. The different effects of W- from Cr- and Mo-promoters on the conversion were observed and are discussed.