A highly efficient silver doped Cu/HMS catalyst was prepared via a co-ammonia evaporation method for the synthesis of ethanol by methyl acetate (MA) hydrogenation. The catalysts were characterized by X-ray diffraction, N-2 adsorption-desorption, H-2 temperature-programmed reduction, fourier-transform infrared spectroscopy, transmission electron microscopy, energy dispersive spectroscopy-mapping, N2O titration, Auger electron spectroscopy and X-ray photoelectron spectroscopy. The characterization results confirmed that introducing appropriate silver to Cu/HMS catalysts improved the dispersion of copper and achieved the Cu-Ag intermetallic nanoparticles. In addition, the interaction between Ag and Cu species increased the ratio of Cu+/(Cu-0+Cu+), which enhanced the adsorption of MA, so as to promote the conversion of MA and ethanol selectivity. Over the Cu1Ag/HMS catalyst, MA conversion and ethanol selectivity reached 94.4% and 88.5%, respectively.