To develop a membrane electrode assembly (MEA) with lower Pt loading and higher performance in proton exchange membrane fuel cells (PEMFCs), it is an important research issue to understand interfacial structure of Pt/C catalyst and ionomer and design the catalyst layer structure. In this study, we prepared short-side-chain Nafion-based ionomer dispersion using propylene glycol (PG) as a solvent instead of water which is commonly used as a solvent for commercially available ionomers. Cathode catalyst layers with different ionomer content from 20 to 35 wt% were prepared using the ionomer dispersion for the fabrication of four different MEAs, and their fuel cell performance was evaluated. As the ionomer content increased to 35 wt%, the performance of the prepared MEAs increased proportionally, unlike the commercially available water-based ionomer, which exhibited an optimum at about 25 wt%. Small size micelles and slow evaporation of PG in the ionomer dispersion were effective in proton transfer by inducing the formation of a uniformly structured catalyst layer, but the low oxygen permeability problem of the PG-based ionomer film should be resolved to improve the MEA performance.