3,5-Bis(bromomethyl)pyridine hydrobromide and 3,5-bis(bromobutyl)pyridine hydrobromide were synthesized from commercially available 3,5-lutidine. The poly(N-alkylation) of these monomers readily yielded new hyperbranched polyelectrolytes. The progress of reaction was followed by 1H NMR. A second-order kinetic scheme fits the experimental data. Rate constants and activation parameters were determined, showing the higher reactivity of 3,5-bis(bromomethyl)pyridine hydrobromide. This was explained by the electron-attractive effect of pyridinium groups on the CH2Br end groups. The structures of the hyperbranched poly[3,5-bis(alkylene)pyridinium]s were investigated by 1H and 13C NMR spectroscopy and a preliminary study of their properties is reported.