: To enhance the performance of a MEA (membrane electrode assembly) in a polymer electrolyte membrane fuel cell (PEMFC), optimum contents of Nafion ionomer as electrolyte in the 20 and 40 wt% Pt/C used in electrodes were examined. Variety characterization techniques were applied to examine optimum Nafion contents: cell performance test, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). According to Pt wt% supported on carbon support, it has been observed that polarization, ohmic, and mass transfer resistances were changed so that the cell performance was significantly dependent on the content of Nafion ionomer. Optimum Nafion ionomer contents in the 20 wt% Pt/C and 40 wt% Pt/C were showed 35 wt% and 20 wt%, respectively. This is due to different surface area of the Pt/C catalyst, and formation of triple phase boundary seems to be affected by the Nafion contents.