This chapter reviews recent advances in the synthesis of polyelectrolytes. New results are presented for linear polymers with stiff and flexible backbones and with star-shaped and randomly branched structures. Block and graft copolymers containing both charged ionic and hydrophobic monomer units are also discussed. Homo- and block copolymers of carbobetaines complete the variation of molecular architecture. Synthetic approaches mainly use anionic, controlled radical, and macromonomer polymerization techniques, and the Suzuki reaction, to synthesize reactive precursors which are subsequently transformed into the final products. Results from physicochemical characterization of the new polymers are also mentioned.