In this study, we present the synthesis and the characterization of novel functionalized arylene main-chain ionomers based on perfluoro-p-xylene (PFX). The polymers were prepared by polycondensation of PFX and 4,4'-dihydroxybiphenyl or bisphenol 2,2-bis(4-hydroxyphenyl)-hexafluoropropane (bisphenol AF). After polymerization, the PFX unit was still able to undergo nucleophilic aromatic substitution reaction, which was used to introduce phosphonic acid groups into the polymer via a reaction with tris(trimethylsilyl)phosphite. Furthermore, electrophilic sulfonation of these polymers was possible in the bisphenol unit when using H2SO4/SO3 as the sulfonation agent. The so-obtained water-soluble PFX-based polyelectrolytes showed excellent chemical stability and were blended with polybenzimidazoles. The blend membranes formed flexible and mechanically robust films with excellent chemical and thermal stabilities.