The asymmetric porous polybenzimidazole membranes were prepared to increase the doping level of phosphoric acid to increase ionic conductivity, to block the fuel/oxidant gas permeation to keep open circuit potential and to maintain chemical and mechanical stability to have good durability for proton exchange membrane fuel cells. The poly(benzimidazole) was synthesized and the asymmetric porous membranes were prepared by pore forming agents and proprietary film formation technology. As a result, it showed higher ionic conductivity, low gas permeability and similar chemical and mechanical stability.