Poly(arylene ether) main-chain phosphonium ionomers were successfully synthesized and characterized. The reaction scheme involved first preparing the poly(arylene ether phosphine oxide) by a nucleophilic step or condensation polymerization of bisphenolates on activated aryl halides, wherein phenyl phosphine oxide was the activating group. High-molecularweight, tough, film-forming polymers were produced with glass transition temperatures of 200°C or higher. The resulting materials were successfully reduced using phenylsilane in refluxing chlorobenzene. The derived phosphine or phosphine/phosphine oxide copolymer was reacted with alkyl halides to produce the phosphonium salts. The resulting materials showed enhanced hydrophilicity and in some cases could be successfully dispersed in water. In addition, chromophores such as Methyl Orange and Methyl Red were combined with the backbone ionomer to produce new film-forming, ionically linked species. The materials are of general interest for situations where water-dispersible intermediates, e.g. coatings, fiber sizings etc. are required. The phosphonium salts can be converted back to the phosphine oxide in fairly high yields by simple thermal methods and in quantitative yield by chemical methods (e.g. the Wittig reaction).