It was demonstrated that adsorbed CO is obtained from the reduction of NaHCO3 solution when Pt(100), Pt(110), disordered Pt(111) and polycrystalline electrodes are employed. Reduction of CO2 coming from the dissociation of the hydrogencarbonate anion is proposed as the reaction that produces CO. By using Fourier transform infrared spectroscopy, linear and multi-bonded CO were detected on polycrystalline platinum electrodes. The shape of the band associated with linearly adsorbed CO is monopolar as a consequence of the partial overlapping, at lower wavenumbers, of the absolute bands at both potentials (0.05 and 0.35 V).