Membrane electrode assemblies (MEAs) are critical components in influencing the electrochemical performance of high-temperature proton exchange membrane fuel cells (HT-PEMFCs). MEA manufacturing processes are mainly divided into the catalyst-coated membrane (CCM) and the catalyst-coated substrate (CCS) methods. For conventional HT-PEMFCs based on phosphoric acid-doped polybenzimidazole (PBI) membranes, the wetting surface and extreme swelling of the PA-doped PBI membranes make the CCM method difficult to apply to the fabrication of MEAs. In this study, by taking advantage of the dry surface and low swelling of a CsH5(PO4)2-doped PBI membrane, an MEA fabricated by the CCM method was compared with an MEA made by the CCS method. Under each temperature condition, the peak power density of the CCM-MEA was higher than that of the CCS-MEA. Furthermore, under humidified gas conditions, an enhancement in the peak power densities was observed for both MEAs, which was attributed to the increase in the conductivity of the electrolyte membrane. The CCM-MEA exhibited a peak power density of 647 mW cm−2at 200 °C, which was ~16% higher than that of the CCS-MEA. Electrochemical impedance spectroscopy results showed that the CCM-MEA had lower ohmic resistance, which implied that it had better contact between the membrane and catalyst layer.