1IntroductionIn direct methanol fuel cells (DMFCs) the methanol crossover from anode to cathode through the polymer electrolyte membrane is a major isue, because this not only causes loss of fuel, but also reduces the performance at the cathode due to the mixed reaction of methanol oxidation with oxygen reduction reaction. Membranes that show high proton conductivity, and at the same time, low methanol permeability are strongly desired but difficult to attain, because of trade-off relations between these parameters. We here report a new type of cost-effective polymer blend membranes based on chemically cross-linked poly(vinyl alcohol) (PVA)and 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS) which is called semi-interpenetrating polymer networks (semi-IPNs). The membrane structure is finished by cross-linking the hydroxyl groups of poly (vinyl alchol) (PVA) main chain with acetal ring formation using glutaraldehyde (GA) cross-linker. For improving the flexibility of the membranes, we reported "binary chemcial cross-linking", "hydrophobicizer" and "stabilizer"effect[1-3], respectively, in our recent work.