Anhydrous nafion-benzimidazole (bz) blend membranes were prepared by room temperature and autoclave solution processing. The physico-chemical properties of anhydrous nafion-bz blend membranes using different solution processing were investigated by TG-DTA, dynamic elastic modulus, XRD, SAXS, and proton conductivity. The nafion-bz blend membrane using autoclave solution processing improved the properties such as a flexibility, density, homogeneity and dynamic elastic modulus, while the crystalline in a macroscopic crystal structure and proton conductivity was nearly the same. (C) 2010 Elsevier B.V. All rights reserved.