The synthesis of three series of double hydrophilic block copolymers (DHBCs), consisting of poly(ethylene oxide) as the neutral water soluble block and a second polyelectrolyte block of variable chemistry, is described. The synthetic scheme involves the anionic polymerization of poly(p-tert-butoxystyrene-b-ethylene oxide) (PtBOS-PEO) amphiphilic block copolymer precursors followed by the acidic hydrolysis of the hydrophobic poly(p-tert-butoxystyrene) (PtBOS) block to an annealed anionic polyelectrolyte poly(p-hydroxystyrene) (PHOS) block. The PHOS block was subsequently transformed into a high charge density annealed cationic polyelectrolyte namely poly[3,5-bis(dimethylaminomethylene) hydroxystyrene] (NPHOS), via amino-methylation. Finally, the NPHOS block was transformed into a quenched polyelectrolyte, namely quaternized poly[3,5-bis(dimethylaminomethylene) hydroxystyrene] (QNPHOS) block by reaction with CH3I. The solution properties of the different series of the above block polyelectrolyte copolymers have been investigated using static, dynamic and electrophoretic light scattering, turbidimetry, and fluorescence spectroscopy. (c) 2007 Wiley Periodicals, Inc.