Biphenyl was grafted on rigid-rod aromatic poly(p-phenylenesulfonic acids) (IEC similar to 8 mequiv g(-1)) to generate cross-linkable polyelectrolytes. Cross-linking conditions and film properties before and after cross-linking were studied. Films equilibrated between 20 and 30% relative humidity (RH) had tensile moduli of 2 to 1 GPa and broke at 5 to 9% elongation. The moduli decreased as RH increased and dropped drastically at high humidity if the films were not cross-linked. Grafted films had conductivities at 80 degrees C 4-5 times that of Nafion NR-212 over the whole relative humidity range even after cross-linking. The sample reported in detail here had a conductivity of 0.10 S cm(-1) at 120 degrees C and 30% RH. As is usual for this class of materials, even after the loss of 24% of starting sulfonic acid groups by grafting and cross-linking, ionic conductivity was high at low humidity. A membrane electrode assembly (MEA) prepared with this rigid-rod poly(phenylenesulfonic acid) proton exchange membrane and tested in a fuel cell exhibited performance and properties similar to those of Nafion NR-212 films. The power density was similar to 95% of that of the Nafion MEA over the operating range in spite of relatively high hydrogen crossover due to the presence of nanocracks in the membrane.