A series of novel polymerized ionic liquids (PILs) contained imidazolium, poly (2,5-bis{[6-(1-butyl-3-imidazolium)hexyl] oxy carbonyl}styrene salts) (denoted as P1X, XBr, BF4, PF6 and TFSI) were successfully synthesized via radical polymerization. The chemical structures of the monomers and their corresponding PILs were confirmed by 1H NMR, 13C NMR, and Fourier transform infrared spectroscopy. Thermogravimetric analysis results showed that these PILs had excellent thermal stability. The phase transitions and liquid-crystalline (LC) behaviors of these polymers were investigated by differential scanning calorimetry, polarized light microscopy (PLM), and wide-angle X-ray diffraction. The combined experimental results showed that all the PILs could form hexagonal columnar (phi H) LC ordered structures because of the strong interaction between the anions and cations in the side groups except for P1TFSI. The conductivities of monomers and PILs were sketchily investigated, and monomers had higher conductivities than those of conprespoding PILs. For comparison, we have synthesized a polymer without counter-anion, but similar to the chemical structure of P1X, poly (2, 5-bis{[6-(4-butoxy-4-oxy phenyl) hexyl] oxycarbonyl} styrene) (denoted as P2). In this case, phenyl took place of imidazolium of side chain, and LC ordered structure did not form. The comparison between P1X and P2 suggested that ion played an important role in the constructing of LC ordered structure. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 1912-1923