The relation between the phase separated morphologies and their transport properties in the polymer blend membrane for direct methanol fuel cell application was studied. In order to enhance the proton conductivity and reduce the methanol crossover, sulfonated poly(arylene ether sulfone) copolymer, with a sulfonation of 60 mol% (sPAES-60), was blended with nonsulfonated poly(ether sulfone) copolymer (RH-2000, Solvay). Various morphologies were obtained by varying the drying condition and the concentration of the casting solution (10, 15, 20 wt%). The transport properties of proton and methanol molecule through the polymer blend membranes were studied according to the absorbed water. AC impedance spectroscopy was used to measure the proton conductivity and a liquid permeability measuring instrument was designed to measure the methanol permeability. The state of water in the blend membranes was confirmed by differential scanning calorimetry and was used to correlate the morphology of the membrane with the membrane transport properties.