The radiation hardening of various UV curable resins provides a simple but powerful method. to fabricate thin films or membranes with desirable physical and chemical properties. In this study, we proposed to use this method to fabricate a novel proton exchange membrane (PEM) for direct methanol fuel cells (DMFC) with good mechanical, transport and stability properties. The PEM was prepared by crosslinking a mixture of a photoinitiator, a bifunctional aliphatic urethane acrylate resin (UAR), a trifunctional triallyl isocyanate (TAIC) crosslinker and tertrabutylammonium styrenesulfonate (SSTBA) to form a uniform network structure for proton transport. Key PEM parameters such as ion exchange capacity (IEC), water uptake, proton conductivity, and methanol permeability were controlled by adjusting the chemical composition of the membranes. The IEC value of the membrane was found to be an important parameter in affecting water uptake, conductivity as well as the permeability of the resulting membrane. Plots of the water uptake, conductivity, and methanol permeability vs. IEC of the membranes show a distinct change in the slope of their curves at roughly the same IEC value which suggests a transition of structural changes in the network. It is demonstrated that below the critical IEC value, the membrane exhibits a closed structure where hydrophilic segments form isolated domains while above the critical IEC value, it shows an open structure where hydrophilic segments are interconnected and form channels in the membrane. The transition from a closed to an open proton conduction network was verified by the measurement of the activation energy of membrane conductivity. The activation energy in the closed structure regime was found to be around 16.5 kJ mol(-1) which is higher than that of the open structure region of 9.60 mol(-1). The membranes also display an excellent oxidative stability, which suggests a good lifetime usage of the membranes. The proton conductivities and the methanol permeabilities of all membranes are in the range of 10(-4) to 10(-2) S cm(-1) and 10(-8) to 10(-7) cm(2) s(-1), respectively, depending on their crosslinking density. The membranes show great selectivity compared with those of Nafion(R). The possibility of using this PEM for DMFC devices is suggested. (C) 2007 Elsevier B.V. All rights reserved.