The electrocatalytic reduction of carbon dioxide (CORR) to ethanol (CHOH) represents notable research significance and commercial value in large-scale chemical production. However, the limited selectivity for CHOH and the uncontrollable changes in active sites during reaction process restrict the ability of catalyst to achieve stable and efficient CORR to CHOH at industrial current density. Here, we report a system that immunizes the reconstruction of catalytic active sites, where the CuAg catalytic centers are protected by nitrilotriacetic acid (NTA). Importantly, the constructed CuAg@NTA catalyst exhibits low barriers for C-C coupling and hydrogenation of *CHCHO to *CHCHO. Consequently, the catalyst achieves a high ethanol faradaic efficiency (FE) of 87.21% with a partial current density of -218.03 mA cm. Furthermore, the catalyst maintaining over 70% of FE after 300 h at -250 mA cm, which are leading among previously reported catalysts in the selectivity and stability of CORR to CHOH at industrial current density. This study provides insights into the selectivity and stability enhancement of catalysts for electrocatalytic CORR to CHOH.