A series of thermotropic main-chain liquid crystalline copolyesters P1-P5 containing 2-(6-oxide-6H-dibenz < c,e >< 1,2 > oxaphosphorin-6-yl)-1,4-dihydroxyphenylene (ODOPB) as non-mesogenic unit and 4,4'-dihydroxybiphenyl (DB) as mesogenic unit were prepared by polycondensation with sebacoyl chloride. The thermal and mesogenic properties were characterized by differential scanning calorimetry (DSC), polarizing optical micrography (POM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). It was found that introducing of ODOPB into polyester decreased the melting temperature (Tm) and the isotropic temperature (Ti). The copolyesters P1-P5 exhibited mesomorphic properties even when the molar ratio of the non-mesogenic monomer ODOPB to mesogenic monomer DB reached 6:4 in feed. For explaining the effect of DOPO group on the mesomorphic properties, the X-ray diffraction analysis of a low molecular weight modal compound containing ODOPB was carried out and the results show that the DOPO side-group is parallel with the most-adjacent benzene ring in the main-chain, which reveals the small effect of ODOPB on the mesogenic structure of polyesters. The thermal analysis showed that the incorporation of phosphorus-containing moieties increase the residual char of the formed liquid crystalline polymers. The thermal stability, however, decreases because the O=P-O bond is less stable than the common C-C bond. (C) 2009 Elsevier Ltd. All rights reserved.