The electrochemical reduction of carbon dioxide (CO2RR) has attracted enormous interest because of the energy crisis and climate change; however, more efficient catalysts are required for practical applications. Herein, we present electrospinning as a facile strategy to synthesize a three-dimensional network of carbon nanofibers embedded with Cu and CeOx nanoparticles (Cu/CeOx@CNFs) as a CO2RR catalyst. The Cu-CeOx interface produced using this method offers synergistic geometric and electronic effects which optimize the adsorption strength of reaction intermediates for the electroreduction of CO2 to CO. In a flow cell configuration, a current density of 100 mA cm(-2) and a CO faradaic efficiency of 59.2% can be obtained at -0.60 V vs. RHE.