A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of β-butyrolactone (β-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which were prepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (Ma = 2000, 4000 and 6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterized by IR, 1H-NMR and GPC.