A series of mesogen-jacketed liquid crystalline polymers, poly{2,5-bis-[(4-alkoxyphenyl)aminocarbonyl]styrene} (P-Cm, where m is the number of carbon atoms in the alkoxy groups, and m = 1, 4, 8, 12), with an amide core and flexible tails of varying lengths on the two ends in the side chain were designed and successfully synthesized via conventional radical polymerization. The mesophase structures of these polymers were dependent on the number of carbon atoms in the peripheral chains. Wide-angle X-ray diffraction and polarized light microscopy results revealed that the polymers with m >= 4 could form smectic A phases, while a columnar nematic phase could be formed for the polymer with methoxy end groups (P-C1). The hydrogen bonding among the side-chain amide groups might play an important role in forming and stabilizing these liquid crystalline phases, which was suggested by the results from variable-temperature FTIR and 2D IR analyses.