Most of Proton Exchange Membrane Fuel Cells (PEMFCs) use the Nafion as electrolyte, which has a limitation in the operating temperature. Usually, these cells operate up to 80??C since the proton conduction is dependent on water molecules carriers. The increase in the operating temperature of a PEMFC cell is desired due to the contribution of the temperature in the acceleration of the electrochemical reactions, which are thermoactivated processes. In the context of searching alternative polymeric electrolytes, PBI (polybenzimidazole) membranes have been considered a promising membrane for high temperature operating PEMFC (HT-PEMFC) due to the combination of satisfactory proton conduction in conditions of low relative humidity (RH) and excellent thermal stability. Pure PBI membranes were prepared by casting a solution of PBI / N, N'-dimethylacetamide (DMAc) and doped with phosphoric acid at different times (1, 3, 5, 7 10 and 15 days). Each membrane was evaluated in Fuel Cell tests, doping level and online Raman tests in order to determine effects of doping level, chemical degradation and fuel cell performance. The electrodes were optimized by studying different catalytic layer composition and the cell tested at different operational conditions.