This paper analyzes the effects of methanol and water vapor on the performance of a high temperature proton exchange membrane fuel cell (HT-PEMFC) at varying temperatures, ranging from 140 °C to 180 °C. For the study, a H3PO4 – doped polybenzimidazole (PBI) – based membrane electrode assembly (MEA) of 45 cm2 active surface area from BASF was employed. The study showed overall negligible effects of methanol-water vapor mixture slips on performance, even at relatively low simulated steam methanol reforming conversion of 90%, which corresponds to 3% methanol vapor by volume in the anode gas feed. Temperature on the other hand has significant impact on the performance of an HT-PEMFC. To assess the effects of methanol-water vapor mixture alone, CO2 and CO are not considered in these tests. The analysis is based on polarization curves and impedance spectra registered for all the test points. After the performance tests, endurance test was performed for 100 h at 90% methanol conversion and an overall degradation rate of −55 μV/h was recorded.