A series of comb-like polymers, poly{2,5-bis[(4-octadecyloxyphenyl) oxycarbonyl]-styrenes} (P-OC18s) with different molecular weights (M-n) and low molecular weight distributions have been successfully synthesized via atom transfer radical polymerization. The phase behaviors have been investigated by a combination of techniques including differential scanning calorimetry, polarized optical microscopy, wide-angle X-ray diffraction, and temperature-variable FTIR spectroscopy. One hand, phase behaviors of the alkyl tails were strongly influenced by the mesogens of polymers, leading to the poor packing of the alkyl tails and the low melting. The other hand, the liquid crystalline phase structures of polymers were found to be strongly M-n dependent. The samples with M-n <= 4.6 x 10(4) formed a smectic phase in low temperature and an isotropic phase in high temperature. The samples with M-n >= 5.2 x 10(4) displayed a reentrant isotropic phase, which was separating the smectic phase and columnar nematic phase. Meantime, the experiment results showed that the glass temperature and the transition temperature from smectic phase to isotropic phase both slightly increased with the increase of MnS; however, the transition temperature from isotropic phase to columnar phase sharply decreased with the MnS improved. The reappearance of isotropic phase is due to the competing between the driving force of the enthalpy and the driving force of the entropy. (C) 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 924-935