In this paper, we designed and synthesized five novel reversible addition-fragmentation chain transfer (RAFT) agents bearing naphthyl moieties in the Z or R groups, including 3,4,5-trimethoxy-benzyl dithio-2-naphthatenoate (TOBDN), 4-nitrobenzyl dithio-2-naphthalenoate (NBDN), 1-menaphthyl 4-cyanodithiobenzoate (NCDB), 1-menaphthyl dithiobenzoate (NDB) and 1-menaphthyl dithio-2-naphthalenoate (NDN). The RAFT polymerizations of styrene mediated by these RAFT agents with AIBN as the initiator at 80 degrees C were conducted and evaluated. Except for NCDB, the RAFT agents showed good control over the polymerization at different RAFT agent concentrations: the M-n,M-GPC increased linearly with the monomer conversion, and the PDIs of the polymers were relatively low (PDI = 1.20-1.50). The structure of RAFT agents bearing three different R groups with naphthyl as the Z group showed less effects on the polymerization rate, while those bearing different Z groups with 1-menaphthyl as the R-center dot group presented significant effects on the polymerization rates. The polymerization rate with phenyl as the Z group was higher than that with 2-naphthyl as the Z group, and it decreased significantly when using 4-cycno phenyl as the Z group. Retardation effects were observed with all the RAFT agents. H-1 NMR spectra and chain extension results confirmed that most of the polymer chains were "living". Ultraviolet (UV) absorption of naphthyl moieties at the R-center dot group showed blue shifts compared with those of naphthyl at the Z group. The UV absorption intensity of PS was uniformly lower than that of the corresponding RAFT agent, while the fluorescence intensity of PS was higher than that of the corresponding RAFT agent. (C) 2009 Elsevier Ltd. All rights reserved.