Electrochemical carbon dioxide and carbon monoxide (CO) reductions offer promising ways to produce high-value alcohols, such as n-propanol, but efficient and selective conversion requires improved catalysts. Here we show that incorporating silver onto oxide-derived copper facilitates the conversion of CO to alcohols with 75.7% selectivity, including 48.8% toward n-propanol, during pulsed-mode electrolysis. The basis for the selectivity enhancements appears to be the tunable hydroxide surface adsorption enabled synergistically by Ag and pulsing, which balances the bound CO configurations, as well as the decreased degree of hydrogen binding to interfacial water that benefits the Langmuir-Hinshelwood hydrogenation route. For illustration, the catalyst was integrated into the cathode of a continuous-flow electrolyzer operating with hydrogen oxidation at the anode, which reduced CO to multicarbon alcohols with a Faradaic efficiency of 66.7% (including 40.4% n-propanol) over the course of 116 h. The coherent control over the adsorption configuration of key intermediates and the interfacial water structure will advance electrochemical conversion technology for alcohol production.