AbstractThe interaction between polydiallyldimethylammonium chloride (PDADMAC) and KI or KBr, followed by changes in conformation of macromolecules, coil compaction, and counterion exchange, was detected by means of turbidimetry and viscometry. In aqueous solutions at presence of KI, PDADMAC rapidly binds iodine by the formation of polymer–iodine complexes PDADMA I− Im (m ≤ 4). Spectrophotometric investigations of the interaction in water without KI prove the formation of complexes of polyquaternary ammonium chloride or bromide with iodine only via iodide. These ions can be generated in the polymer‐catalyzed hydrolysis reaction of iodine. By inducing hydrolysis of iodine and binding the eventually formed iodide, PDADMAC acts as an iodine acceptor with self‐strengthening capacity. For the sorption of gaseous iodine, the possibility of direct interaction of its dipoles with the charged groups of the polyelectrolyte is also reasoned. Polydiallyldimethylammonium halides were used to modify activated carbon and employed in a nuclear power station for treatment of outlet gases containing radioactive iodine. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2710–2716, 2006