4l-A2B2 star-shaped copolymers contained polystyrene (PS), poly(isoprene) (PI), poly(ethylene oxide) (PEO) or poly(e-caprolactone) (PCL) arms were synthesized by a combination of Glaser coupling with living anionic polymerization (LAP) and ring-opening polymerization (ROP). Firstly, the functionalized PS or PI with an alkyne group and a protected hydroxyl group at the same end were synthesized by LAP and then modified by propargyl bromide. Subsequently, the macro-initiator PS or PI with two active hydroxyl groups at the junction point were synthesized by Glaser coupling in the presence of pyridine/CuBr/N,N,N0,N00,N00-penta-methyl diethylenetri-amine (PMDETA) system and followed by hydrolysis of protected hydroxyl groups. Finally, the ROP of EO and e-CL monomers was carried out using diphenylmethyl potassium (DPMK) and tin(II)-bis(2-ethylhexanoate) (Sn(Oct)2) as catalyst for target star-shaped copolymers, respectively. These copolymers and their intermediates were well characterized by SEC, 1H NMR, MALDI-TOF mass spectra and FTIR in details.