The twin-tail tadpole-shaped (cyclic polystyrene)-block-[linear poly (tert-butyl acrylate)]2 [(c-PS)-b-(l-PtBA)2] was synthesized by combination of Glaser coupling reaction with atom transfer radical polymerization (ATRP) and living anionic polymerization (LAP). First, the telechelic PS with an active and an ethoxyethyl-protected hydroxyl groups at both ends was prepared by LAP of St monomers using lithium naphthalenide as initiator and terminated by 1-ethoxyethyl glycidyl ether. And the alkyne groups were introduced onto each PS end by selectively reaction of active hydroxy group with propargyl bromide in NaH/tetrahydrofuran (THF) system. Then, the intramolecular cyclization was carried out by Glaser coupling reaction in pyridine/Cu(I)Br system in air atmosphere. Finally, the macroinitiator of c-PS with two bromine groups at the junction point was synthesized via the cleavage of ethoxyethyl group and the subsequent esterification of the deprotected hydroxyl groups with 2-bromoisobutyryl bromide. The copolymer of (c-PS)-b-(l-PtBA)2 was obtained by ATRP of tBA monomers, and the PtBA segment was also hydrolyzed for (cyclic polystyrene)-block-(linear polyacrylic acid)2 [(c-PS)-b-(l-PAA)2]. The target copolymers and all intermediates were well characterized by GPC, MALDI-TOF MS, and 1H NMR in detail. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012