AbstractElectrochemically converting CO₂ to valuable chemicals holds great promise for closing the anthropogenic carbon cycle. Owing to complex reaction pathways and shared rate‐determining steps, directing the selectivity of CO₂/CO electrolysis to a specific multicarbon product is very challenging. We report here a strategy for highly selective production of acetate from CO electrolysis by constructing metal‐organic interfaces. We demonstrate that the Cu‐organic interfaces constructed by in situ reconstruction of Cu complexes show very impressive acetate selectivity, with a high Faradaic efficiency of 84.2 % and a carbon selectivity of 92.1 % for acetate production, in an alkaline membrane electrode assembly electrolyzer. The maximum acetate partial current density and acetate yield reach as high as 605 mA cm⁻² and 63.4 %, respectively. Thorough structural characterizations, control experiments, operando Raman spectroscopy measurements, and density functional theory calculation results indicate that the Cu‐organic interface creates a favorable reaction microenvironment that enhances *CO adsorption, lowers the energy barrier for C−C coupling, and facilitates the formation of CH₃COOH over other multicarbon products, thus rationalizing the selective acetate production.