Ultra-high molecular weight polyethylene (UHMWPE) powder was irradiated by gamma rays using a Co-60 source. Simultaneous and pre-irradiation grafting was performed in air and in inert atmosphere at room temperature. The monomer selected for grafting was styrene, since the styrene-grafted UHMWPE could be readily post-sulfonated to afford proton exchange membranes (PEMs). The effect of absorbed radiation dose and monomer concentration in methanol on the degree of grafting (DG) is discussed. It was found that the DG increases linearly with increase in the absorbed dose, grafting time and monomer concentration, reaching a maximum at a certain level. The order of rate dependence of grafting on monomer concentration was found to be 2.32. Furthermore, the apparent activation energy, calculated by plotting the Arrhenius curve, was 11.5 kJ/mole. Lower activation energy and high rate dependence on monomer concentration shows the facilitation of grafting onto powder substrate compared with film. The particle size of UHMWPE powder was measured before and after grafting and found to increase linearly with increase in level of grafting. FTIR-ATR analysis confirmed the styrene grafting. The grafted UHMWPE powder was then fabricated into film and post-sulfonated using chlorosulfonic acid for the purposes of evaluating the products as inexpensive PEM materials for fuel cells. The relationship of DG with degree of substitution (DS) of styrene per UHMWPE repeat unit and ion exchange capacity (IEC) is also presented. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.