AbstractBimetallic tandem catalysts have emerged as a promising strategy to locally increase the CO flux during electrochemical CO₂ reduction, so as to maximize the rate of conversion to C−C‐coupled products. Considering this, a novel Cu/C−Ag nanostructured catalyst has been prepared by a redox replacement process, in which the ratio of the two metals can be tuned by the replacement time. An optimum Cu/Ag composition with similarly sized particles showed the highest CO₂ conversion to C₂₊ products compared to non‐Ag‐modified gas‐diffusion electrodes. Gas chromatography and in‐situ Raman measurements in a CO₂ gas diffusion cell suggest the formation of top‐bound linear adsorbed *CO followed by consumption of CO in the successive cascade steps, as evidenced by the increasingνC−H bands. These findings suggest that two mechanisms operate simultaneously towards the production of HCO₂H and C−C‐coupled products on the Cu/Ag bimetallic surface.