This study focused on the surface morphology dependence of the carbon dioxide electrochemical reduction reaction (CO2ERR) on copper (Cu) electrodes. Several commercially available Cu foils, configured with different crystal structures, showed different surface morphologies when they were chemically etched or thermally annealed. The CO2ERR activity on the Cu foils was strongly dependent on their surface morphology, which varied with a combination of the surface treatment and their crystal structures.