Neutron reflectometry was used to examine the interactions of polymer electrolyte fuel cell (PEFC) materials that comprise the triple-phase interface. Smooth, idealized layers of Nafion on glassy carbon (GC) and Pt surfaces were used to experimentally model the PEFC electrode interfaces. Different multilayer structures of Nafion were found in contact with the Pt or GC surfaces. These structures showed separate hydrophobic and hydrophilic domains formed within the Nafion layer when equilibrated with saturated D2O vapor. A hydrophobic Nafion region was formed adjacent to a Pt film. However, when Nafion was in contact with a PtO surface, the Nafion at the Pt interface became hydrophilic. The adsorbed oxide layer caused a long-range restructuring of the perfluorosulfonic acid polymer chains that comprise Nafion. The thicknesses of the hydrophobic and hydrophilic domains changed to the same magnitude when the oxide layer was present compared to a thin hydrophobic domain in contact with Pt. A three-layer Nafion structure was formed when Nafion was in direct contact with GC. The findings in this research are direct experimental evidence that both the interfacial and long-range structural properties of Nafion are affected by the material with which it is in contact. Evidence of physical changes of aged Nafion films was obtained, and the results showed a permanent increase in the thickness of the Nafion film and a decrease in the scattering length density (SLID), which are attributed to irreversible swelling of the Nafion film. The aging also resulted in a decrease in the SLID of the GC substrate, which is likely due to either an increase in surface oxidation of the carbon or loss of carbon mass at the GC surface.