The use of aqueous or aqueous methanolic ionene (cationic polyelectrolytes consisting of dimethylammonium charge centers interconnected by alternating alkyl chain segments containing x and y methylene groups) solutions as mobile phases in thin layer chromatography (TLC) is described. The ortho, meta and para isomers of chlorobenzoic acid and phenylphenol as well as dinitroanilines and 1-and 2-naphthol were successfully chromatographed using aqueous solutions of [3,16]-ionene with polyamide thin layer sheets. Some quinones were successfully resolved using this same aqueous ionene mobile phase but with cellulose thin layer plates. For some analytes, the TLC retention results obtained with the In this paper, we introduce a new type of organized assembly (ordered media or pseudophase) which can function as the mobile phase in thin layer chromatographic separations, that of aqueous solutions of Ionenes. Ionenes ([n,m]-ionenes) are linear aliphatic cationic polyelectrolytes consisting of dimethylammonium charge centers interconnected by alternating alkyl chain segments containing n and m methylene groups, respectively.