Electrochemical reduction of carbon dioxide to value-added multicarbon (C2+) products is a promising way to obtain renewable fuels of high energy densities and chemicals and close the carbon cycle. However, the difficulty of C–C coupling and complexity of the proton-coupled electron transfer process greatly hinder CO2 electroreduction into specific C2+ products with high selectivity. Here, we design an electrocatalyst of Sr-doped CuO nanoribbons with a hydrophobic surface for CO2 electroreduction to ethane with high selectivity. Sr doping enhances the chemical adsorption and activation of CO2 by inducing oxygen vacancies and increasing *CO coverage by stabilizing Cu2+ active sites, thus further boosting subsequent C–C coupling. The hydrophobic surface with dodecyl sulfate anions (DS–) adsorption increases the oxophilicity of the catalyst surface, enhancing the conversion of the *OCH2CH3 intermediate to ethane. As a result, the optimized Sr1.97%–CuO exhibits a Faradaic efficiency of 53.4% and a partial current density of 13.5 mA cm–2 for ethane under a potential of −0.8 V. This study provides a strategy to design a Cu-based catalyst by alkaline earth metal ions doping with the hydrophobic surface to engineer the evolution of the intermediates for a desired product during CO2RR.
