On the study of high temperature proton exchange membrane (HTPEM), the trade-off between proton conductivity and physico-chemical property (such as mechanical strength, dimensional stability and methanol resistance) remained a main obstacle for comprehensive performance enhancement. To address this issue, novel HTPEM was prepared by doping phosphotungstic acid intercalated ferric sulfophenyl phosphate (FeSPP-PWA) into polybenzimidazole (PBI) via hot pressed method. Intense hydrogen bonding network was built between PBI and FeSPP-PWA, rendering construction of proton channels and reinforcement of physico-chemical property. As a novel proton conductor, FeSPP-PWA facilitated formation of efficient proton transfer pathway. The layered morphology and inorganic intrinsity of FeSPP-PWA also improved the mechanical and dimensional stability while reducing the methanol permeability of the PBI/FeSPP-PWA membranes. The composite membrane exhibited good thermal stability up to 200 degrees C. The proton conductivity of PBI/FeSPP-PWA (30 wt%) reached 110 mS cm(-1) at 170 degrees C and 100% RH, and was 69.3 mS cm(-1) at 180 degrees C and 50% RH. The PBI/FeSPP-PWA also showed low methanol permeability and high membrane selectivity for application in direct methanol fuel cells. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.