The synthesis, characterization, and some properties of new copolyesters of poly(butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) based on L-arabinitol and xylitol are described. These copolyesters were obtained by polycondensation reaction in the melt of mixtures of 1,4-butanediol or ethylene glycol and 2,3,4-tri-O-benzyl-L-arabinitol or 2,3,4-tri-O-benzyl-xylitol with dimethyl terephthalate. Their weight-average molecular weights ranged between 7000 and 55,000, with polydispersities ranging from 1.4 to 4.7. Copolymers containing 1,4-butanediol could be analyzed by NMR, and were found to have a statistical microstructure. All these copolyesters were thermally stable, with degradation temperatures well above 300 degrees C. With increasing amounts of alditol in the copolyester, the melting temperature and crystallinity decreased in both series, and the glass transition temperature increased for the PBT series and decreased for the PET series. Only PBT-derived copolyesters containing a maximum of 10% alditol units showed discrete scattering characteristic of crystalline material. No substantial differences in either structure or properties were observed between the L-arabinitol and xylitol copolyester series. (C) 2008 Wiley Periodicals, Inc.