Anionic ring-open polymerization of ethylene oxide (EO) functionalized 1-hydroxy-2-methoxybenzene (HMOB) monomer 1-(2,3-epoxypropyl)-2-methoxybenzene (EPMOB) led to the formation of the precursor polymer oligo(1-(2,3-epoxypropyl)-2-methoxybenzene) (OEPMOB). Poly(OEPMOB-co-1-hydroxy-2-methoxybenzene) films P1, P2, P3, and P4 were successfully achieved by secondary electrochemical copolymerization of the monomer mixtures OEPMOB/HMOB with different mass ratios of 3:1, 2:1,1:1, and 1:2, respectively. The possibility of inter- and intramolecular polymerization resulted in a cross-linking conjugated network microstructure. A series of experiments were carried out to investigate the influence of monomer mass ratios on the electrochemical copolymerization and other properties of copolymer films. UV-vis, FT-IR, and H-1 NMR were used to characterize the structure of copolymers. Fluorescence spectroscopic studies revealed that the copolymers partly dissolved in DMSO were all good blue light-emitters, with strong emissions at 392 nm in the doped state. Since EO and HMOB units were introduced into the skeletal backbone, thermal stability of copolymers was improved in comparison with their corresponding homopolymers. (C) 2012 Elsevier Ltd. All rights reserved.