Some new polybenzimidazoles (PBIs) containing different acidic groups (-SO3H and-PO3H2) as proton donors and amphoteric groups (imidazole and-PO3H2) as proton transmitters were synthesized. The proton conductivity was 0.015 S. cm(-1) for PBI1 and 0.075 S.cm(-1) for PBI2 at ambient temperatures in water. At 140 degrees C and RH = 30%, the proton conductivity equaled 0.126 S.cm(-1) for PBI2 and 0.003 S-cm(-1) for Nafion. Moreover, PBI2 showed high proton conductivity under anhydrous conditions at 140 degrees C. It exhibited a porous morphology due to its sulfonated hydrophilic side chains. Theoretical studies showed that hydrogen bonding (HB) interactions of side chains and main chain groups leads to the formation of pores in the polymer structure. The presence of pores and hydrophilic groups in polymer structure increases water uptake and the durability of water molecules at high temperatures. The formation of a great HB network between acidic and amphoteric groups helps proton transport under anhydrous conditions.