The RAFT polymerization of styrene in bulk was carried out using tetraethylthiuram disulfide (TETD) as an initiator and 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as a chain transfer agent at different temperatures. The results of the polymerization showed that TETD could initiate the RAFT polymerization of styrene in the living way. The kinetics of the polymerization showed first order. The molecular weights of the polymers increased linearly with conversions and were close to the theoretical values (M-n,M-th). The polydispersities of the polymers remained relatively narrow (< 1.3). The structure of the polymer was characterized by H-1 NMR. The result showed that there were moieties of CPDN and TETD attained at the end of the polymer. Using these double functional end capped polymers, the chain-extension experiments were successfully carried out not only in the conventional RAFT polymerization way, but also under UV irradiation. (c) 2005 Elsevier Ltd. All rights reserved.