A series of non-mesogenic vinyl monomers, 2,5-bis(alkoxycarbonyl)styrene, were synthesized and polymerized via free radical polymerization. The alkoxy groups were systematically varied to investigate the effects of their size and architecture on the thermotropic liquid-crystalline properties of the resultant polymers. Although no traditional mesogen was present in the macromolecular structure, all the polymers revealed stable hexagonal columnar liquid-crystalline phase at the temperatures well above their glass transitions when the molecular weights were high enough, as evidenced by a combinatory analysis of differential scanning calorimetry, polarized light microscopy, and one- and two-dimensional wide-angle X-ray diffraction techniques. For the polymers containing five carbon atoms in the alkoxy terminals, the temperatures of glass transition and mesophase formation decreased and the d-spacing value of mesophase increased as the methyl substituent moved away from the connecting phenyl ring. Increasing the number of methyl group or the size of the substituent had the same effect. In the case of polymers with Y-shaped alkoxy terminals, the larger the side groups, the lower the glass-transition temperature and mesophase formation temperature and the larger the d-spacing value of mesomorphic structure. (C) 2008 Elsevier Ltd. All rights reserved.