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A series of poly{2,5-bis[(4-butoxyphenyl)-oxycarbonyl]styrenes} (PBPCS) with low molecular weight distribution was synthesized by atom transfer radical polymerization (ATRP). The mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and rheometer. PBPCS showed the phase transition from isotropic into liquid crystal (LC) phase, and the LC phase formed at high temperature and disappeared in the subsequent cooling procedure. Using the WAXD fiber pattern, the phase structure of the PBPCS at higher temperature showed hexagonal columnar nematic phase. Experimental results demonstrated that the driving force of the entropy is an important factor during the unusual LC phase formation of PBPCS.