Porous poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) membranes were prepared by solvent-nonsolvent evaporation technique. Morphology and porosity of the membranes were varied with different nonsolvents and had an effect on electrochemical properties. The porous membranes were functionalized with different liquid electrolyte solutions such as p-toluene sulfonic acid/phosphoric acid/sulfuric acid. Maximum electrolyte uptake and minimal electrolyte leakage were tailored by the optimized porosity of the membranes. Thermal behavior obtained in this study ensures the complete evaporation of nonsolvents and ensures its thermal stability. The pTSA-activated PVdF-HFP/THF membrane exhibited high ionic conductivity of about 27.27 mS/cm and a lower methanol permeability in the range of 9.7 x 10(-8) cm(2)/s. High compatibility between pTSA solution and porous PVdF-HFP polymer electrolyte membrane enhances its electro chemical behavior than that of conventional liquid electrolytes. (c) 2008 Elsevier B.V. All rights reserved.