The semi-interpenetrating (semi-IPN) membrane composed of crosslinked sulfonated polystyrene (SPS) within the host blend of PVdF-co-HFP (Polyvinylidenefluoride-co-hexafluoropropylene) and Naflon has already been tested as a promising polymer electrolyte membrane (PEM) in terms of improved water uptake, proton conductivity and electrical efficiency for application in the direct methanol fuel cell (DMFC). These desired results have generated further curiosity about a fine tuning between the contents of divinyl benzene (DVB) as a crosslinker and azobisisobutyronitrile (AIBN) as an initiator for the optimization of PEM characteristics. It has been observed that an increase in AIBN content leads to an acceptable degree of water uptake, swelling ratio and proton conductivity in PEM, while higher DVB content causes declined methanol crossover, leading to higher membrane selectivity. These two opposing effects are optimized in terms of proton conductivity, tensile strength and membrane selectivity for the membrane consisting of 0.4 wt% of AIBN and 1.2 wt% of DVB. Moreover, the maximum power density obtained for the membrane having optimum selectivity is 56 mW cm(-2), when analyzed at 90 degrees C. These results indicate that one can achieve a high power density in comparison to Nafion by fine tuning the contents of initiator and cross-linker during the synthesis of the semi-IPN membrane. (C) 2015 Elsevier B.V. All rights reserved.