Although poly(L-lactic acid) (PLLA) can be greatly toughened by copolymerization, its lower melting temperature and lower ability of crystallization limit its widespread application as commodity. In order to improve the melting point and ability of crystallization of PLLA based multiblock copolymers, Poly (D-lactic acid) (PDLA) oligomer was used to complex with PLLA-bisphenol A epoxy resin multiblock copolymer (PLLA-co-bis A) to form a stereocomplex. Differential scanning calorimeter (DSC), X-ray diffraction (XRD) and polarized optical microscopy (POM) were used to characterize the thermal properties and crystallization behavior of the stereocomplexes. The results indicated that the stereocomplex of PLLA-co-bis A and PDLA was formed. The formed stereocomplexes with good thermal properties (high T-m) and good crystallization properties (high crystallization rate and more stable crystals) are convinced to have high potential as high performance biodegradable polymers. (c) 2006 Elsevier Ltd. All rights reserved.