Phosphoric acid doped polybenzimidazole (PBI) is the most common membrane material for high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC). The PBI membrane is usually doped by immersion in hot phosphoric acid. Immersion time and acid temperature affect the doping level of the membrane. In this work we studied the influence of doping time and temperature on the ex-situ and in-situ proton conductivities of poly (2, 5-benzimidazole) (AB-PBI) membranes as well as the fuel cell performance. Confocal Raman microscopy was employed to spatially resolve the acid distribution within the AB-PBI membranes. Therefore the interactions between the basic nitrogen-sides of the AB-PBI polymer and the phosphoric acid protons were investigated. We found that membranes with a 6 h doping time had significantly higher proton conductivity than those doped for only 3 h. In terms of absolute acid up-take, however, the difference was rather small. This result shows that the doping level alone does not define the conductivity of the membrane. The conductivity is also influenced by the micro acid distribution within the membrane. Highest membrane conductivity and fuel cell performance with fumapem AM cross-linked membranes were achieved with a doping time of 6 h and a doping temperature of 120 degrees C. (C) 2014 Elsevier B.V. All rights reserved.