A series of radiation‐grafted cation‐ and anion‐exchange polymers have been studied with the intent of developing procedures for dissolving and film casting these polymers. Solvent swelling studies have shown that these polymers display two maxima in plots of solvent uptake vs. solvent solubility parameter. While similar behavior is shown by the ion‐exchange polymer Nafion, the anion‐ and cation‐exchange polymers studied here will not dissolve under conditions (developed by us) which dissolve Nafion. We believe that this insolubility results from covalent cross‐links and/or enhanced crystallinity in the chain‐material regions of these polymers. These polymers do, however, swell extensively in certain solvents at high temperatures, and suspensions may be prepared from the swollen polymer. We have cast films from these suspensions onto electrode surfaces and report initial results of electrochemical characterization of these films.