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A series of triarmed poly(propylene oxide)-poly(D-lactide)-poly(L-lactide) stereoblock copolymers (PPO-PDLA-PLLA) with different D/L molar ratios were synthesized via ring opening polymerization from PPO,DLA and LLA.By means of fourier transform infrared (FTIR),nuclear magnetic resonance (NMR),gel permeation chromatography (GPC),Differential scanning calorimeter (DSC) and wide-angle X-ray diffractometer (WAXD),the chemical structures,molecular weight,thermal properties and crystal structures were studied for these synthesized PPO-PDLA prepolymer and PPO-PDLA-PLLA stereoblock copolymers.