Abstract: The Cu-Mo/C catalyst was prepared with ammonium molybdate tetrahydrate and copper nitrate trihydrate, and used for the selective hydrodeoxygenation reaction of methyl oleate. The catalysts were characterized by X-ray diffraction, X-ray diffraction photoelectron spectroscopy and electron paramagnetic resonance spectroscopy. The optimal process for the preparation of biodiesel from methyl oleate catalyzed by Cu-Mo/C and the catalytic performance of Cu-Mo/C were investigated. The results of the study showed that the addition of Cu promoted the formation of Mo/C catalyst and the Mo₂C and MoO₂ component in the catalyst worked together. The oxygen vacancies on the MoO₂ component could preferentially adsorb the C=O bond in the substrate and then Mo₂C component hydrodeoxygenated it, avoiding the hydrogenation of C=C bond. The excellent performance of catalyst and the selectivity of unsaturated hydrocarbons were achieved. The conversion rate of methyl oleate reached 98.8%, and the selectivity of unsaturated hydrocarbons was 40.2% at reaction temperature of 280 ℃, hydrogen pressure of 2.5 MPa and reaction time of 3 h. The catalytic activity of Cu-Mo₁₀/C was comparable to the noble metal Pd and commercial Mo/C catalysts, while the unsaturated hydrocarbon selectivity was higher as well as the good stability.