A polymer electrolyte membrane composed of polystyrene sulfonic acid (PSSA) crosslinked within a poly(vinylidene fluoride) (PVDF) matrix is provided. This membrane exhibits low methanol crossover which translates to higher fuel and fuel cell efficiencies. A fuel cell comprising a PSSA-PVDF membrane is also provided. Further, methods of decreasing the fuel crossover rate, enhancing fuel cell efficiency, and enhancing electrical performance of a fuel cell are provided.