The competitive adsorption of Nafion functional groups induce complex potential dependencies (Stark tuning) of vibrational modes of CO adsorbed (CO(ads)) on the Pt of operating fuel cell electrodes. Operando infrared (IR) spectroscopy, polarization modulated IR spectroscopy (PM-IRRAS) of Pt-Nafion interfaces, and attenuated total reflectance IR spectroscopy of bulk Nafion were correlated by density functional theory (DFT) calculated spectra to elucidate Nafion functional group coadsorption responsible for the Stark tuning of CO(ads) on high surface area fuel cell electrodes. The DFT calculations and observed spectra suggest that the side-chain CF3, CF2 groups (i.e., of the backbone and side chain) and the SO3(-) are ordered by the platinum surface. A model of the Nafion-Pt interface with appropriate dihedral and native bond angles, consistent with experimental and calculated spectra, suggest direct adsorption of the CF3 and SO3(-) functional groups on Pt. Such adsorption partially orders the Nafion backbone and/or side-chain CF2 groups relative to the Pt surface. The coadsorption of CF3 is further supported by Mulliken partial charge calculations: The CF3 fluorine atoms have the highest average charge among all types of Nafion fluorine atoms and are second only to the sulfonate oxygen atoms.