Ionic cluster mimic, polymer electrolyte membranes were prepared using polymer composites of crosslinked poly(vinyl alcohol) (PVA) with sulfated- β-cyclodextrins ( β-CDSO3H) or phosphated- β-cyclodextrins ( β-CDPO(OH)2). When Nafion, developed for a fuel cell using low temperature, polymer electrolyte membranes, is used in a direct methanol fuel cell, it has a methanol crossover problem. The ionic inverted micellar structure formed by micro-segregation in Nafion, known as ionic cluster, is distorted in methanol aqueous solution, resulting in the significant transport of methanol through the membrane. While the ionic structure formed by the ionic sites in either β-CDSO3H or β-CDPO(OH)2 in this composite membrane is maintained in methanol solution, it is expected to reduce methanol transport. Proton conductivity was found to increase in PVA membranes upon addition of ionized cyclodextrins. Methanol permeability through the PVA composite membrane containing cyclodextrins was lower than that of Nafion. It is thus concluded that the structure and fixation of ionic clusters are significant barriers to methanol crossover in direct methanol fuel cells.