Quaternization and dequaternization of tertiary amine compounds were employed to obtain thermally reversible ionene networks from aqueous colloidal polymer dispersions prepared via emulsion polymerization. Chlorine-functionalized polymers prepared via the emulsion copolymerization of styrene (St), butylacrylate (BA), or both with chloromethylstyrene, and amino-functionalized polymers prepared via the emulsion copolymerization of St, BA, or both with 2-(dimethylamino)ethylacrylate or 4-vinylpyridine, were reacted without polymer separation, with a ditertiaryamine crosslinker and a dihalide crosslinker, respectively, to obtain crosslinked polymers. Crosslinked polymers were also obtained via the reaction of a chlorine-functionalized polymer dispersion with an amino-functionalized polymer dispersion or via the drying of the polymer blend prepared from the two kinds of dispersions. Reactive solubility experiments, flowability investigations (by thermocompression at ca. 215 Β°C), IR, and 1 H NMR analyses of the obtained crosslinked polymers indicated that the generated ionene bridges dequaternized on heating and requaternized on cooling. In comparison with solution crosslinking, no organic solvent was employed, and simple procedures were required for the preparation of the thermally reversible covalent crosslinked polymers.