A series of silver modified Cu/SiO2 catalysts were synthesized with ammonia-evaporation method and applied in vapor-phase hydrogenation of methyl acetate to ethanol. The influence of additive 'Ag' on the structural evolution of catalyst was systematically studied by several characterization techniques, such as N-2 adsorption-desorption, N2O titration, PXRD, HER, in-situFTIR, H-2-TPR, H-2-TPD, XPS and TEM. Results showed that incorporation of a small amount of Ag could enhance the structural stability, and the strong interaction between Cu and Ag species was conducive to increase the dispersion of copper species and create a suitable Cu+/(Cu-0 + Cu+) ratio, which was proposed to be responsible for the improved catalytic activity. The maximum conversion of MA (94.1%) and selectivity of ethanol (91.3%) over optimized Cu-0.5Ag/SiO2 and 120 h on stream without deactivation under optimal conditions demonstrates its excellent stability. (C) 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.