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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°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 …