The behavior of sulfonated poly (ether ether ketone) (SPEEK) with different degrees of sulfonation (DS) (60-76%) blended with charged surface modifying macromolecule (cSMM) at different operating temperatures as an electrolyte membrane for direct methanol fuel cell (DMFC) application has been studied. A good DMFC electrolyte membrane should possess high proton conductivity and low methanol permeability. In this work, the fabricated SPEEK/cSMM membranes were compared with pure SPEEK and commercial Nafion 112 membranes in terms of water uptake, proton conductivity, and methanol permeability at temperature range of room to 80 degrees C The water uptake of SPEEK/cSMM membranes increased with the temperature and it was higher than that of SPEEK and Nafion 112 membranes; however newly fabricated membranes with 68% and 76% DS were dissolved at high temperatures although showed the same trend at lower temperatures. In agreement with the result of water uptake, proton conductivity of SPEEK/cSMM membranes also increased with temperature and was higher as compared to the corresponding SPEEK membranes; however it was still lower than that of Nafion 112. The methanol permeability values of the SPEEK/cSMM membranes were lower at different temperatures as compared to corresponding SPEEK and Nafion 112 at the same condition. Owing to considerable proton conductivity and lower methanol permeability values, SPEEK60/cSMM exhibited the highest overall performance than other tested membranes at 60 degrees C. These results indicated that SPEEK60/cSMM membrane is promising to be used as a polymer electrolyte membrane in direct methanol fuel cell. (C) 2013 Elsevier B.V. All rights reserved.