Nafion ยฎ ionomer content of the cathode catalyst-layer of a polymer electrolyte fuel cell (PEFC), made by the "decal" hot pressing method, has been investigated for its effect on performance and structure of the membrane electrode assembly (MEA). Varying Nafion ยฎ content was shown to have an effect on performance within the entire range of polarization curves (i.e. kinetic, ohmic, and mass-transport regions) as well as on the structure. AFM analysis shows the effect of Nafion on the dispersion of carbon aggregates. Further analysis using TEM demonstrates the effect of Nafion on both the dispersion of carbon aggregates and the distribution and thickness of the Nafion ionomer films surrounding the catalyst/carbon aggregates. The MEA structure change correlates well with the MEA performance on both kinetics and mass-transport region. The determining factors on the performance of MEA are the interfacial zone (between the ionomer and catalyst particle), the dispersion of catalyst/carbon aggregates and the distribution/thickness of Nafion films. An optimized Nafion ยฎ content in the range of 27 ยฑ 6 wt.% for the cathode was determined for an E-TEK 20% Pt 3 Cr/C catalyst at a loading of 0.20 mg Pt/cm 2 .