Thermosensitive gel is synthesized through controlled/"living" free radical copolymerization of styrene and DVB mediated by an alkoxyamine inimer, 2,2,6,6-tetramethyl-1-(1 '-phenylethoxy)-4-(4 '-vinyl-benzyloxy)-piperidine (V-ET). The inimer plays the role of both incorporating "T-shaped" inter-chain linkages and mediating the polymerization. First order kinetics is observed for crosslinking polymerizations before gel point, indicating a constant concentration of propagating radicals. Monomer conversion at the gel point depends on the feed ratio of DVB to V-ET. Higher amount of V-ET results in later gel point due to smaller molecular weight of the primary chains that depends inversely on the concentration of nitroxide. The resulting gel contains permanent and labile crosslinking points formed by DVB units and alkoxyamine moieties, respectively. Therefore, the gels exhibit gel-sol transition within a narrow temperature range. The gel properties, such as the swelling ratio and gel-sol transition temperature, can be controlled by changing the feed ratio of DVB to V-ET. The microenvironments in different gels, or at different temperatures, are investigated by ESR spectroscopy. (C) 2010 Elsevier Ltd. All rights reserved.