Abstract Exploratory studies of three polyelectrolytes containing several types of ionic species in different molecular environments were performed by dynamic mechanical, dielectric, and calorimetric methods. The materials were dimethyldiallyl-ammonium chloride (DMDAAC), 3-acrylamido-3-methylbutyl trimethylammonium chloride (AMBTAC) and sodium 2-acrylamido-2-methylpropanesulfonate (AMPS). It was found that the glass transition temperature of the polyanionic material is higher than that of polycationic materials, which correlates with the charge to internuclear distance (q/a) effect. In all of the materials studied, it was observed that the glass transition shifts to lower temperatures, and that the tan δ peak height increases with increasing plasticizer content. However, the general pattern of Tg depression is quite different for the polycationic polymers than for the anionics, as is shown by comparing the results of this work with several previous studies. For water-plasticized DMDAAC, which was studied ...