A series of poly(ester imide ketone)s derived from N,N'-hexane-1,6-diylbis(trimellitimide), 4,4'-dihydroxybenzophenone, and p-hydroxybenzoic acid (PHB) were synthesized by the direct polycondensation method in benzene sulfonyl chloride, dimethylformamide, and pyridine with varied PHB contents. The liquid crystalline behavior and thermal properties of the poly(ester imide ketone)s were characterized by polarized-light microscopy, wide-angle X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and temperature-modulated differential scanning calorimetry (MDSC). The results showed that the synthesized polymers possessed a nematic thermotropic liquid crystalline characteristic and high thermal stability. The liquid crystalline polymers, with a PHB content ranging from 0 to 50 mol %, exhibited multiple phase transitions as evidenced by the MDSC results. A transitional smectic phase from solid state to nematic thermotropic liquid crystalline state was observed, and a transition model is proposed. Under certain conditions, the polymer with 33 mol % PHB content showed two significantly different liquid crystalline textures. This type of liquid crystalline polymer exhibited excellent fiber forming. (C) Wiley Periodicals, Inc.