The structure of electrochemical intermediates of methanol oxidation on platinum in aqueous sulfuric acid has been investigated under steady state conditions using polarization modulation Fourier transform infrared reflection absorption spectroscopy. Terminally bonded and bridge‐bonded are observed in the cathodic to anodic sequence. However, only bridge‐bonded is observed in the anodic to cathodic sequence. The conventionally assumed C‒O‒H group was not observed. The spectroscopic results are compared with similar information obtained by means of radiotracer and potentiodynamic techniques. A new mechanism is proposed which is intended to apply to the steady‐state situation and may differ from that pertaining to potential sweep data.