Hexafluoropropylidene polybenzimidazole (F6PBI) was synthesized with excellent chemical stability and improved solubility. When doped with phosphoric acid, however, the F6PBI membranes showed plastic deformation at elevated temperatures. Further efforts were made to covalently crosslink F6PBI membranes with chloromethyl polysulfone as a polymeric crosslinker. Comparing with linear F6PBI and mPBI membranes, the polymer crosslinked F6PBI membranes exhibited little organo solubility, excellent stability towards the radical oxidation, high resistance to swelling in concentrated phosphoric acid solutions, and improved mechanical strength, especially at elevated temperatures. The superior characteristics of crosslinked membranes allowed for higher acid doping levels and therefore increased proton conductivity as well as significantly improved fuel cell performance and durability, as compared with the linear F6PBI and mPBI membranes.