Adsorbed CO Stark tuning rates have been studied for the first time in direct methanol fuel cells on Pt black catalysts supported only on the polymer electrolyte (Nafion) in membrane electrode assemblies. The bipolar peaks resulting from the Stark shift of CO absorbance peaks are inverted, indicating an anomalous increase in the reflectivity where CO infrared absorption occurs. The vibrational Stark tuning data suggests that CO oxidation occurs on the perimeter of COads islands, which is consistent with the formation of CO within and above Pt double layer potentials as reported by Kunimatsu. This is expected since methanol is continuously delivered to the anode at all potentials in direct methanol fuel cells.