A mesogen-jacketed liquid crystal polymer,poly{2,5 -bis[(4′-hexyloxyphenyl)oxycarbonyl]styrene}(PHPCS),with number-average d molecular weight of 1.28×105 and polydispersity of 1.48 was prepared vi a 2,2,6,6 -tetramethyl-piperidinyloxy mediated free radical polymerization.The thermotr opic behavior was studied by a combination of differential scanning calorimetry, thermogravimetry,polarized optical microscope and wide-angle X-ray diffracti on.PHPCS was not crystalline over the entire temperature region studied.On hea ting,PHPCS first became an isotropic melt at glass transition temperature (T g) and then a mesophase at temperatures much higher than T g.On subseq uent cooling,the formed ordered phase disappeared above T g.Contrary to t heoretical predictions and previous experimental observations,the transition fr om isotropic melt to liquid crystalline phase was an endothermic process and th e order-disorder transition took place with concurrence of heat release.