The electroreduction of CO 2 to valuable fuels or high-value chemicals by using sustainable electric energy provides a promising strategy for solving environmental problems dominated by the greenhouse effect. Copper-based materials are the only catalysts that can convert CO 2 into multicarbon products, but they are plagued by high potential, low selectivity, and poor stability. The key factors to optimize the conversion of CO 2 into multicarbon products are to improve the adsorption capacity of intermediates on the catalyst surface, accelerate the hydrogenation step, and improve the C−C coupling efficiency. Herein, we successfully doped Lewis acid Mg into Cu-based materials using a simple liquid-phase chemical method. In situ Raman and FT-IR tracking show that the Mg site enhances the surface coverage of the *CO intermediate, simultaneously promoting water dissociation. Under an industrial current density of 0.7 A cm −2 , the FE C2+ reaches 73.9 ± 3.48% with remarkable stability. Density functional theory studies show that doping the Lewis acid Mg site increases the coverage of *CO and accelerates the splitting of water, thus promoting the C−C coupling efficiency, reducing the reaction energy barrier, and greatly improving the selectivity of C 2+ products.