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We synthesize polybenzimidazole (PBI; Mw= 1.65×105 g mol-1,Mw/Mn= 2.32) and benzyl phosphoric acid grafted PBI (PBI-BP; 24 mol.% degree of grafting).PBI-BP is highly dissolved in 85 wt.% H3PO4 aqueous solution.We show that blending PBI-BP in the PBI membrane increases the membrane H3PO4 doping level and improves the membrane proton conductivity when the PBI-BP content in the blend membrane is lower than 40 wt.%.