To replace Nafion type perfluorosulfonated polymers, non-sulfonated hydrocarbon-based polybenzimidazole (PBI) derivatives have been prepared for a polymer electrolyte fuel cell (PEFC) membrane. The PBI membranes are easily doped with strong inorganic acid to get proton conductivity. They perform as a PEFC membrane at high temperature (120~200℃) under non-humidified condition. The PBI derivatives are very promising materials for proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC).