Copolyesters of p,p'-bibenzoic acid, dimer acid, and an alkylene glycol are prepared by melt polycondensation of of dimethyl p,p'-bibenzoate, dimer acid, and an alkylene glycol. The copolyesters are characterized by the inherent viscosity, FTIR, proton NMR, DSC, polarized microscopy, and X-ray diffraction. The polymer composition and sequence distribution of the copolyesters can be seen from the NMR spectra. The copolyesters exhibit a degree of randomness of about 1, indicating that they are random copolymers. The glass-transition temperature (T-g) and the melting point (T-m) of the copolyesters are found from the DSC heating curves. When the content of the flexible dimer acid unit increases, the T-g of the copolyesters decreases significantly. The copolymerization effect decreases the crystallinity and the T-m of the copolyesters. It can be seen from the DSC, polarized microscopy, and X-ray diffraction data that some copolyesters derived from 1,6-hexanediol and 1,5-pentanediol exhibit a monotropic smectic phase. As the molar content of the dimer acid unit increases, the isotropicmectic transition temperature and the smectic order decreases significantly. The liquid crystallinity is completely destroyed at certain molar contents of the dimer acid unit. The smectic order of the copolyesters derived from 1,6-hexanediol is significantly higher than that of the copolyesters derived from 1,5-pentanediol, and it is described as an odd-even effect. (C) 2003 Wiley Periodicals, Inc.