The electroreduction of CO₂ has recently achieved notable progress in the formation of C₂ products such as ethylene and ethanol. However, the direct synthesis of C₃ products is considerably limited by the C₂–C₁ coupling reaction and the faradaic efficiency has remained low. Here we present a supersaturation strategy for the electrosynthesis of 2-propanol from CO₂ in highly carbonated electrolytes. By controlling the CO₂ concentration above the saturation limit, we have developed a co-electrodeposition method with suppressed galvanic replacement to obtain a CuAg alloy catalyst. In supersaturated conditions, the alloy achieved high performance for the production of 2-propanol with a faradaic efficiency of 56.7% and at a specific current density of 59.3 mA cm⁻². Our investigations revealed that the presence of dispersed Ag atoms in Cu weakens the surface binding of intermediates in the middle position of the alkyl chain and strengthens the C–O bonds, which favours the formation of 2-propanol over 1-propanol.