The invention provides a system and a process that allow for the selective electrochemical conversion of carbon dioxide to carbon monoxide with high energy efficiency, using a cathode comprised of bismuth in combination with an anode such as an anode comprised of platinum. The electrolysis system may be comprised of a single or two compartment cell and may employ an organic electrolyte or an ionic liquid electrolyte. The invention permits the storage of solar, wind or conventional electric energy by converting carbon dioxide to carbon monoxide and liquid fuels.