Series of mesogenic biphenol derivatives HO6OPPOn (n = 4,6,8) were prepared by asymmetric reaction and purified. Then HOLAxO6OPPOn were prepared with controlled molecular weights by adjusting the feed ratios of HO6OPPOn, SnOct(2) catalyst and LEA by Ring-Opening Polymerization. P-AOLAxO6OPPOn materials were obtained in high yields by the free radical polymerization of polymerizable macromonomers of AOLAxO6OPPOn synthesized by esterization of HOLAxO6OPPOn with acrylic acid in the presence of DCC/DMAP. Their molecular weights were characterized by H-1 NMR and GPC. Differential Scanning Calorimeter method and Polarized Optical Microscopy method were used to study their thermal behaviors. Both AOLAxO6OPPOn and P-AOLAxO6OPPOn materials are found to form LCs with increased T-g, T-m and T-i with longer O-LLA segment length. Polymerization of AOLAxO6OPPOn also resulted in the increase of T-g, T-m, and T-i. X-ray diffraction measurements revealed the presence of smectic phase in these materials. The O-LLA segments are in helical structure from CD spectra and this makes the resulting polymer materials good candidate of optical materials for huge optical rotation power. (C) 2010 Elsevier Ltd. All rights reserved.