Cationic polyelectrolytes with pyridinium and 1,2-dimethylimidazolium functionalities based on a hyperbranched polyglycerol scaffold with a narrow polydispersity were prepared by a polymer analogous reaction in a one-pot synthesis. By the variation of the spacer lengths between the cationic functionalities and polyether scaffold, a simple method was developed to adjust the charge density and flexibility of the polycations, as reflected by their glass-transition temperature. The polyelectrolytes were further characterized in detail by H-1 NMR, C-13 NMR, and IR spectroscopy, as well as thermogravimetric analysis. (c) 2005 Wiley Periodicals, Inc.