A series of mesogen-jacketed liquid crystalline polymers, poly{2,2,3,3,4,4,4-heptafluorobutyl 4'-hydroxy-2-vinylbiphenyl-4-carboxylate} (PF3Cm, where m is the number of carbon atoms in the alkoxy groups, and m 1, 4, 6, and 8), the side chain of which contains a biphenyl core with a fluorocarbon substituent at one end and an alkoxy unit of varying length on the other end, were designed and successfully synthesized via atom transfer radical polymerization. For comparison, poly {butyl 4'-hydroxy-2-vinylbiphenyl-4-carboxylate} (PC4Cm), similar to PF3Cm but with a butyl group instead of the fluorocarbon substituent, was also prepared. Differential scanning calorimetric results reveal that the glass transition temperatures (T(g)s) of the two series of polymers decrease as m increases and T(g)s of the fluorocarbon-substituted polymers are higher than those of the corresponding butyl-substituted polymers. Wide-angle X-ray diffraction measurements show that the mesophase structures of these polymers are dependent on the number of the carbon atoms in the fluorocarbon substituent and the property of the other terminal substituent. Polymers with fluorocarbon substituents enter into columnar nematic phases when m >= 4, whereas the polymer PF3C1 exhibits no liquid crystallinity. For polymers with butyl substituents, columnar nematic phases form when the number of carbon atoms at both ends of the side chain is not equal at high temperatures and disappear after the polymers are cooled to ambient temperature. However, when the polymer has the same number of carbon atoms at both ends of the side chain, a hexagonal columnar phase develops, and this phase remains after the polymer is cooled. (C) 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 557-564