Ni-W-B and La-promoted Ni-W-B amorphous catalysts were prepared by chemical reduction and applied, within the hydrodeoxygenation (HDO) of phenol. The resulting catalysts were characterized by surface area, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results showed that some of the electrons were transferred from B-0 to Ni-0 in Ni-W-B amorphous catalyst. La promoted the reduction of Ni2+ to Ni-0 and increased the WO3 content on the catalyst surface. Adding appropriate La in Ni-W-B amorphous catalyst improved the amorphous degree of the catalyst, but excess amounts of La covered some active sites and decreased the catalyst surface area. The HDO of phenol on these amorphous catalysts proceeded via the hydrogenation dehydration route, leading to no benzene in the products, which could meet the standard of clear fuel in European regulation. La-Ni-W-B amorphous catalysts exhibited higher activities in the HDO of phenol than Ni-W-B amorphous catalyst.