A new method for the synthesis of biodegradable multifunctional group-terminated copolymers is explored, by which a series of novel biodegradable tetra-amino-terminated PLGA telechelic copolymers are synthesized for the first time. The composition, structure, and thermal property of the telechelic copolymer were characterized by FTIR, NMR, GPC, and MDSC. The results show that by careful selection of the synthesis parameters, tetra-amino-terminated PLGA telechelic copolymer with desired molecular weight and glass transition temperature can be prepared. This versatile synthetic platform can provide a large family of biodegradable, tetra-amino-terminated telechelic copolymers with tunable physiochemical and biological properties useful for the preparation of network biodegradable polyester elastomer with tailorable properties.