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Copper‐based catalysts electrochemically convert CO₂ into multicarbon molecules. However, the selectivity toward alcohol products has remained relatively low, due to the lack of catalysts favoring the adsorption of key intermediates in the alcohol pathways. Herein, a Cu₃Ag₁ electrocatalyst is developed using galvanic replacement of an electrodeposited Cu matrix. The Cu₃Ag₁ electrocatalyst enables a 63% Faradaic efficiency for CO₂‐to‐alcohol production and an alcohol partial current density of −25 mA cm⁻² at −0.95 V versus reversible hydrogen electrode, corresponding to a 126‐fold enhancement in selectivity and 25‐fold increase in activity compared to the bare electrodeposited Cu matrix. Density functional theory calculations reveal that the interphase electron transfer from Cu to Ag generates electron‐deficient Cu sites and favors the adsorption of CO₂ reduction intermediates in the alcohol pathway …