A facile synthetic strategy for preparing hydroxylated polymethacrylate amphiphilic block copolymers (PCzMMA-b-PBMMA, PFlMMA-b-PBMMA) incorporated with primary and secondary hydroxyl groups and electroactive moieties along the polymer backbone is reported. Full characterization, structure-property relationship and self-assembly of these polymers are discussed. Due to interplay of hydrophobic/hydrophilic interactions, PCzMMA-b-PBMMA formed a layered lattice and PFlMMA-b-PBMMA showed a vesicular morphology. Electropolymerization of the electroactive units led to the formation of cross-conjugated polymer network in solution and in thin films. The network structure was characterized with a range of spectroscopic techniques. Such highly processable polymers may be of interest to applications in which a conducting amphiphilic films with strong adhesion to various substrates are required. (C) 2014 Wiley Periodicals, Inc.