In heterogeneous hydrogenation reactions, the influence of water on catalytic performance is substantial, often exerting a negative impact due to competitive adsorption with reactants or intermediates. In this investigation, ZnO was introduced into the Cu/SiO2 catalyst to alleviate adverse effects of water, stemming from its preferential adsorption on active Cu+ sites. The modifications in textural properties were monitored using various characterization techniques, including H2-TPR, N2O titration, BET, and TEM. The experimental findings, coupled with analyses utilizing XRD, XPS, UV–Vis and in-situ DRIFT, elucidated that high Cu+ contents were not responsible for catalytic performance improvement, while the enhanced localization of the d-orbitals for Cu+ and surface synergism between active Cu0 and surface Zn(1+δ)+–OV–Zn(1+δ)+ were pivotal in mitigating adverse impacts of water. Specifically, the enhanced localization of the d-orbitals for Cu+ sites diminished the adsorption capacity of water molecule on Cu+ sites, and surface synergism introduced new active sites for the adsorption and dissociation of ethyl acetate. Their combined effect mitigated the adverse effects of water on catalytic performance at relative low reaction temperature. Among the investigated catalysts, the Cu/SiO2-IZn catalyst, where ZnO was doped through the incipient impregnation method, showed superior hydrogenation performance. It manifested a growth rate of 257.2 %, outperforming the Cu/SiO2 catalyst under optimal reaction conditions with water. In essence, this study makes a substantial contribution to comprehending and refining catalyst design for effective hydrogenation processes in the presence of water.