 Abstract electrochemical CO2 reduction, CO2R, is a promising method for closing the carbon cycle for chemical synthesis. Pressurizing CO2 from industrial sources can increase its reactivity, leading to higher formate production compared to ambient pressure CO2. Operando techniques such as Raman spectroscopy were used to validate this mechanism and guide the development of a functionalized copper cathode with a proton-resistant layer to further enhance the selectivity effect. This research demonstrates the potential of industrial CO2 as a source of renewable energy for sustainable chemical synthesis.