In this study, a catalyst slurry was prepared with a Pt/C catalyst, Nafion ionomer solution as a binder, an ionic liquid (IL) (1-butyl-3-methylimidazolium tetrafluoroborate), deionized water and ethanol as a solvent for the application to polymer electrolyte fuel cells (PEFCs) at high-temperatures. The effect of the IL in the electrode of each design was investigated by performing a cyclic voltammetry (CV) measurement. Electrodes with different IL distributions inside and on the surface of the catalyst electrode were examined. During the CV test, the electrochemical surface area (ESA) obtained for the Pt/C electrode without ILs gradually decreased owing to three mechanisms: Pt dissolution/redeposition, carbon corrosion, and place exchange. As the IL content increased in the electrode, an ESA decrement was observed because ILs leaked from the Nafion polymer in the electrode. In addition, the CVs under conditions simulating leakage of ILs from the electrode and electrolyte were evaluated. When the ILs leaked from the electrode, minor significant changes in the CV were observed. On the other hand, when the leakage of ILs originated from the electrolyte, the CVs showed different features. It was also observed that the ESA decreased significantly. Thus, leakage of ILs from the polymer electrolyte caused a performance loss for the PEFCs by reducing the ESA. As a result, greater entrapment stability of ILs in the polymer matrix is needed to improve electrode performance.