Starting from MPEG-NH 2 , a series of amphiphilic triblock copolymers MPEG-b-PLL-b-PLA were synthesized through PEG-NH 2 -initiated ring-open polymerization of N ε-benzyloxycarbonyl-L-lysine, followed by acylation coupling between the amino-terminated MPEG-b-PZLL-NH 2 and carboxyl-terminal PLA and the deprotection of amines. The block copolymers were characterized by FT-IR, 1 H NMR, GPC, DSC and TEM. The copolymer functional groups, molecular and block structures were verified by FT-IR, 1 H NMR and DSC, respectively. The GPC results indicate that the chain lengths of each block can be controlled by varying the feed ratios of the monomer and initiator, providing the polymer samples with a narrow molecular weight distribution (M w /M n 01.10~1.25). The TEM analysis shows that the triblock polymers can self-assemble into polymeric micelles in aqueous solution with spherical morphology. The cellcytotoxicity assay indicates that the triblock polymers show no obvious cytotoxicity against Bel7402 human hepatoma cells.