The influence of the amount of polybenzimidazole (PBI)-H3PO4 (normalized with respect to the PBI loading, which expressed as C/PBI weight ratio) content in both the anode and cathode has been studied for a PBI-based high temperature proton exchange membrane (PEM) fuel cell. The electrodes prepared with different amounts of PBI have been characterized physically, by measuring the pore size distribution, and visualizing the surface microstructure. Afterwards, the electrochemical behaviour of the electrodes has been evaluated. The catalytic electrochemical activity has been measured by voltamperometry for each electrode prepared with a different PBI content, and the cell performance results have been studied, supported by the impedance spectra, in order to determine the influence of the PBI loading in each electrode. The best results have been achieved with a C/PBI weight ratio of 20, for both the anode and the cathode. A lower C/PBI weight ratio (larger amount of PBI in the catalytic layer) reduced the electrocatalytic activity, and impaired the mass transport processes, due to the large amount of polymer covering the catalyst particle, lowering the cell performance. A higher C/PBI weight ratio (lower amount of PBI in the catalytic layer) reduced the electrocatalytic activity, and slightly increased the ohmic resistance. The low amount of the polymeric ionic carrier PBI-H3PO4 limited the proton mobility, despite of the presence of large amounts of "free" H3PO4 in the catalytic layer. © 2009 Professor T. Nejat Veziroglu.