We present latest results on the development of a new solid electrolyte for DMFC application. Films are obtained through fluorine-free chemistry consisting of grafting reaction between polyethylene film, preliminary irradiated, and styrene monomers. This reaction proceeds through the formation of hydroperoxide groups activated by ferrous catalyst that initiates the polymerization reaction with styrene. Sulfonic groups are then introduced on the aromatic rings by sulfonation with chlorosulfonic acid. Functional properties of membranes are then characterized out of cell through ion conductivity and methanol permeability measurements. Obtained results are very promising for application in DMFC. (c) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.