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, SnOct2 catalyst and LLA by Ring-Opening Polymerization. P-AOLAxO6OPPOn materials were obtained in high yields by the free radical polymerization of polymerizable macromonomers of AOLAxO6OPPOn