A novel benzodithioate compound with a pyrene structure in the R group, pyrenylmethyl benzodithioate (PMB) was synthesized. Using PMB as the chain transfer agent (CTA), the RAFT polymerizations of styrene with AIBN as ail initiator were carried out in different reaction conditions. The results indicated that PMB was an effective CTA for the RAFT polymerizations of styrene with the "living"/controlled characteristics. The structures of the obtained polymers were characterized by H-1 NMR. The results showed that majority of the polymer chains contained the pyrene moiety in the chain end. The enhanced fluorescence property in CHCl3 solution was observed. The chain-extension experiments of the obtained polystyrene (PS) with the monomers of styrene and methyl acrylate were successfully carried out. (c) 2007 Elsevier Ltd. All rights reserved.