Pore-filling membranes using three monomers, i.e., styrene, N-vinyl pyrrolidone (VP), and divinylbenzene (DVB), are prepared for polymer electrolyte fuel cell (PEFC) applications. A porous polyethylene (PE) film substrate is used to enhance the dimensional stability of the prepared membranes. The proton conductivity and the water uptake of the styrene/VP/DVB membranes are similar to those of the styrene/DVB membranes, even though their ion exchange capacity is slightly lesser than that of the styrene/DVB membranes. Furthermore, the thermal stability of the styrene/VP/DVB membranes is higher than that of the styrene/DVB membranes, and, for the same DVB content, the membranes containing VP exhibit better oxidative stability. VP increases the membrane's water-absorbing ability due to its intrinsic hydrophilic property and decreases weak a-hydrogen derived from the sulfonated styrene. Finally, the membrane-electrode assembly (MEA) using the 80/10/10 (Styrene/VP/DVB in weight percentage) membrane shows better performance than that using the 90/0/10 membrane.