Well-defined flexible, annealed, and quenched polyelectrolytes with two cationic sites per monomeric unit are synthesized. The synthetic scheme involves the synthesis of narrowly distributed poly)-tert-butoxystyrene) precursors by anionic polymerization high vacuum techniques, hydrolysis to poly(p-hydroxystyrene), and Subsequent quantitative functionalization by a Mannich-type reaction, to yield annealed polyelectrolytes with two dimethylamino groups per monomer. In a last step, the dimethylamino groups are converted into quaternary ammonium salts by reaction with methyl iodide to give high-charge-density quenched cationic polyelectrolytes. The polymers are molecularly characterized by NMR and FT-IR spectroscopy, while their solution behavior is studied by potentiometric titrations, turbidimetry, and fluorescence spectroscopy as a function of pH, in the case of the annealed polyelectrolytes, as well as by viscometry in the case of the quenched polyelectrolytes.