Acid-doped polybenzimidazole (PBI) membranes have been demonstrated for fuel cell applications with advanced features such as high operating temperatures, little humidification, excellent CO tolerance, and promising durability. The water uptake and acid doping of PBI membranes have been studied. The water uptake of PBI from the vapour phase is only slightly increased as the atmospheric humidity increases up to unity (100%). Little difference is observed for the water uptake front vapour and liquid phases, behaving very differently from Nafion membranes. When doped with phosphoric acid at low levels (<2), the active sites of the imidazole ring are preferably occupied by the doping acid and the water uptake is consequently lower. At higher acid doping levels, the water uptake is influenced by the excess of hygroscopic acid and higher water uptake than for Nafion membranes is observed. Upon doping, the acid is found to be concentrated inside the polymer. Only two molecules of phosphoric acid are bonded to each repeat unit of PBI, corresponding to the two nitrogen sites available. Infrared and Raman spectra show the presence of strong hydrogen bonds between phosphoric acid and nitrogen atoms of the imidazole rings. The excessive doping acid is "free acid" that contributes to high conductivity but suffers from a fast washing out when adequate liquid is present. (C) 2004 Elsevier B.V. All rights reserved.