Cu/SiO2catalysts, for the synthesis of ethylene glycol (EG) from hydrogenation of dimethyl oxalate (DMO), were prepared by ammonia-evaporation and sol-gel methods, respectively. The structure, size of copper nanoparticles, copper dispersion, and the surface chemical states were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) and N2adsorption. It is found the structures and catalytic performances of the catalysts were highly affected by the preparation method. The catalyst prepared by sol-gel method had smaller average size of copper nanoparticles (about 3-4 nm), better copper dispersion, higher Cu+/C0ratio and larger BET surface area, and higher DMO conversion and EG selectivity under the optimized reaction conditions.