Electrochemical oxidation of vanadium hexacarbonyl anion, V(Co)6 in aprotic solvents results in formation of the V(0) complex which decomposes to form CO in high concentrations next to the electrode surface. As a result, CO is more rapidly adsorbed on the surface than by conventional methods. Surface reflection infrared spectroscopy shows that the potential dependent frequency shift for the infrared active bands due to CO adsorbed on platinum is 19 cm−1/V in 1,2-dichloroethane and 22 cm−1/V in acetonitrile, which are considerably less than the 30 cm−1/V observed in aqueous systems.