Composite membranes of Nation and sulfonated poly(arylene ether sulfone) were prepared. Sulfonated poly(arylene ether sulfone)s with different degrees of sulfonation were blended with Nafion to reduce the methanol crossover. The morphology, proton conductivity and methanol permeability of the resulting composite membranes were investigated by SEM, EDAX, AC impedance spectroscopy and permeability measuring instrument. The cross-sections of the composite membranes showed a phase separated morphology. The morphology and phase separation mechanism could be controlled by varying the blend ratio and the degree of sulfonation of poly(arylene ether sulfone). These complex morphologies can be applied for reducing methanol crossover. The methanol permeability and proton conductivity of the composite membranes were lower than those of Nation 117 membrane since the development of an ionic pathway in the blend membrane was more difficult than that in Nafion itself.