The tadpole-shaped copolymers polystyrene (PS)-b-[cyclic poly(ethylene oxide) (PEO)] [PS-b-(c-PEO)] contained linear tail chains of PS and cyclic head chains of PEO were synthesized by combination of Glaser coupling with living anionic polymerization (LAP) and ring-opening polymerization (ROP). First, the functionalized polystyrene-glycerol (PS-Gly) with two active hydroxyl groups at omega end was synthesized by LAP of St and the subsequent capping with 1-ethoxyethyl glycidyl ether and then deprotection of protected hydroxyl group in acid condition. Then, using PS-Gly as macroinitiator, the ROP of EO was performed using diphenylmethylpotassium as cocatalyst for AB(2) star-shaped copolymers PS-b-(PEO-OH)(2), and the alkyne group was introduced onto PEO arm end for PS-b-(PEO-Alkyne)(2) . Finally, the intramolecular cyclization was performed by Glaser coupling reaction in pyridine/Cu(I) Br/N,N,N',N '',N'-pentamethyldiethylenetriamine system under room temperature, and tadpole-shaped PS-b-(c-PEO) was formed. The target copolymers and their intermediates were well characterized by size-exclusion chromatography, proton nuclear magnetic resonance spectroscopy, and fourier transform infrared spectroscopy in details. The thermal properties was also determined and compared to investigate the influence of architecture on properties. The results showed that tadpole-shaped copolymers had lower T-m, T-c, and X-c than that of their precursors of AB(2) star-shaped copolymers. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 2227-2235, 2012