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A novel biodegradable ABC-shaped star copolymer, poly (ethylene glycol)(PEG)-b-poly (ε-caprolactone)(PCL)-poly-c-poly (ɤ-benzyl-L-glutamic acid)(PBLG)(MPEG-PCL-PBLG), was synthesized by the graft polymerization of MPEG-NH2 with the core of Boc-LYSZ-COOH and the twice ring-opening polymerization (ROP) of ε-caprolactone (CL) and N-carboxyanhydride of ɤ-benzyl-L-glutamate (BLGNCA) with centrally amino-functionalized lysine as a initiator. The ABC-shaped star copolymer and its precursors were characterized by 1H NMR, GPC, and DSC-TG measurements.