Various sulfonated poly (2,6-dimethyl-1,4-phenylene oxide) (SPPO)-polybenzimidazole (PBI) blend membranes were prepared and investigated as proton exchange membranes (PEMs) for direct methanol fuel cell (DMFC) applications. With increasing PBI content water swelling, ion exchange capacity, proton conductivity and methanol permeability of SPPO-PBI membranes were found to be decreased due to acid-base interactions between sulfonate and the amine groups of the blended components. Among various SPPO-PBI blend membranes, 80:20 wt% was found as the optimum composition, which showed the highest membrane selectivity parameter. Direct methanol-air single fuel cell tests revealed a higher cell efficiency of 11.6% for SPPO80-PBI20 than 10.9% for Nafion (R) 117 at 5 M methanol feed, and also a higher power density of 57.6 mW.cm(-2) compared to 39.4 mW.cm(-2) for Nafion (R) 117. Transport properties as well as DMFC performance results of SPPO-PBI blend PEMs converge to indicate their potential for DMFC applications. Copyright (C) 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.