The work focuses on the design, synthesis, and characterization of a series of mesogen-jacketed liquid crystalline polymers (MJLCPs) based on the octyl substituted biphenyl mesogenic core through different linkage groups. The molecular characterizations of the polymers obtained by conventional free radical polymerization were performed with 1H NMR, gel permeation chromatography, and thermogravimetric analysis. Their thermotropic liquid crystalline (LC) behaviors were investigated in detail by a combination of various techniques, such as polarized light microscopy, differential scanning calorimetry, and 1D and 2D wide-angle X-ray diffraction. Our results showed that all the polymers were thermally stable, and their LC phases were greatly dependent on the linking groups between the biphenyl mesogenic core and terminal alkyl group substituent. Polymers with ether/ester or ether linkage group exhibited an unusual phase behavior with temperature increasing, tetragonal columnar nematic LC phase, or columnar nematic phase developed at high temperatures for the polymers transformed into amorphous phase during cooling process, showing a re-entrant phase behaviors. However, polymers with ester linkage group were not LC with temperature varied. It is illustrated that subtle changes in the molecular structure brought about tremendous variation of the LC phase properties for MJLCPs. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 25452554