A new characterization method using a porous plug model was proposed to determine the degree of sulfonation (DS) of ionomer binder with respect to the membrane used in membrane-electrode assemblies (MEAs) and to analyze the fraction of proton pathways through ionomer-catalyst combined electrodes in MEAs for polymer electrolyte fuel cells (PEFCs). Sulfonated poly(ether ether ketone) was prepared to use a polymeric electrolyte and laboratory-made SPEEK solution (5wt.%, DMAc based) was added to catalyst slurry to form catalyst layers. In case of the SPEEK-based MEAs in this study, DS of ionomer binder for catalyst layers should be the same or higher than that of the SPEEK membrane used in the MEAs. The porous plug model suggested that most of protons were via the ionomer binder (${sim}92.5%$) bridging the catalyst surface to the polymeric electrolyte, compared with the pathways through the alternative between the interstitial water on the surface of ionomer binder or catalyst and the ionomer binder (${sim}7.3%$) and through only the interstitial water on the surface of ionomer or catalyst (${sim}0.2%$) in the electrode of the MEA comprising of the sulfonated poly(ether ether ketone) membrane and the 5wt.% SPEEK ionomer binder. As a result, it was believed that the majority of proton at both electrodeds moves through ionomer binder until reaching to electrolyte membrane. The porous plug model of the electrodes of MEAs reemphasized the importance of well-optimized structure of ionomer binder and catalyst for fuel cells.