Membranes composed of poly(vinyl alcohol) (PVA) and a proton source polymer, sulfonated phenolic resin (s-Ph) displayed good proton conductivity of the order of 10(-2) S cm(-1) at ambient temperatures. Upon cross-linking above 110 degrees C, covalent links between the sulfonate groups of the phenolic resin and the hydroxyl groups of the PVA were established. Although this sacrificed certain sulfonate groups, the conductivity value was still preserved at the 10(-2) S cm(-1) level. In sharp contrast to Nafion, the current membrane (both before and after cross-linking) was also effective in reducing the methanol uptake where the swelling ratio decreased with increase of methanol concentration. Although both the methanol permeation and the proton conductivity were lower compared to Nafion, the conductivity/permeability ratio of 0.97 for the PVA/s-Ph is higher than that determined for Nafion. The results suggested the effectiveness of proton transport in the polymer-complex structure and the possibility that a high proton conductivity can be realized with less water. (c) 2006 Published by Elsevier B.V.