Ionic polymers, their blends and composites are considered potential candidates for application as electrolytes in fuel cells. While developing new materials for membranes, it is important to understand the interactions of these electrolytic materials with electrodes/catalysts and with reactants/products. Some of these interactions can be understood by estimating the surface energy and wettability of the membrane materials. In this work, polyvinyl alcohol with varying degrees of sulfonation and its blend with sulfonated poly(ether ether ketone) are prepared and studied for their wettability characteristics using goniometry. The surface energy and its components are estimated using different approaches and compared. Properties such as the ion-exchange capacity, the proton conductivity and the water sorption/desorption behaviour are also investigated to understand the relationship with wettability and surface energy and its components. Among the different methods, the van Oss acid-base and the modified Berthelot approaches yield comparable estimates for the total surface energy. (C) 2010 Elsevier B.V. All rights reserved.