Perfluorinated cobalt phthalocyanine (CoFPc) immobilized on carbon electrodes was found to electrocatalyze the reduction of CO2 selectively to CO in an aqueous solution. The conversion of CO2 became apparent at -0.5 V vs RHE, and the Faradaic efficiency for the CO production reached as high as 93% at -0.8 V vs RHE. Highly stable electrolysis of CO2/H2O into CO/O2 was achieved for 12 h by applying the same catalyst as the cathode for CO2 reduction and the anode for water oxidation. This result indicates the highly robust nature of the CoFPc at wide range of potentials from -0.9 V to +2.2 V vs RHE, demonstrating the potential bipolar electrolytic system for CO2/H2O electrolysis, using the single-site molecular CoFPc-based electrocatalyst, which is simple, inexpensive, robust, and efficient. © 2016 American Chemical Society.