The macro-TEMPO agent (poly(4-glycidyloxy-22,6,6-tetramethylpiperidine-1-oxyl), PGTEMPO) was synthesized by anion ring-opening polymerization (ROP) of 4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (GTEMPO) using potassium t-butoxide as the initiator. The comb-shaped copolymer, PGTEMPO-g-PVBK, was prepared via nitroxide-mediated free radical polymerization (NMP) using PGTEMPO as macro-TEMPO agent and 9-(4-vinylbenzyl)-9H-carbazole (VBK) as the monomer. The polymerizations showed characteristics of "living"/controlled behavior. The optical properties, thermal analysis and electrochemical properties of the comb-shaped copolymers were investigated. The fluorescence and ultraviolet intensity and cyclic voltammetries of the comb-shaped copolymers with different molecular weight showed a regular order. (C) 2010 Elsevier Ltd. All rights reserved.