A set of high-molecular-weight, new, side-chain liquid-crystalline polyethers was obtained by chemical modification of poly(epichlorohydrin) with potassium 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate. The degree of modification depended on the reaction conditions and ranged from 39 to 58%. The highest value was an apparent modification plateau. NMR characterization indicated no side reactions of any kind (e.g., deshydrohalogenation). All random-grafted copolymers had hexagonal columnar mesophases with the exception of the least modified copolymer, which had a nematic columnar mesophase. X-ray diffraction experiments performed on mechanically oriented samples showed that tapered groups were tilted with respect to the column axes. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym. Chem 42: 326 -340, 2004 Keywords: poly(epichlorohydrin); liquid-crystalline polymers (LCP); ionic channel; hexagonal columnar phase; tapered groups; biomimetic; supramolecular structures