The reversible addition-fragmentation chain transfer (RAFT) polymerizations of 2-naphthyl acrylate (2NA) initiated by 2,2 '-azobisisobutyronitrile were investigated with 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as a RAFT agent at various temperatures in a benzene solution. The results of the polymerizations showed that 2NA could be polymerized in a controlled way by RAFT polymerization with CPDN as a RAFT agent; the polymerization rate was first-order with respect to the monomer concentration, and the molecular weight increased linearly with the monomer conversion. The polydispersities of the polymer were relatively low up to high conversions in all cases. The chain-extension reactions of poly(2-naphthyl acrylate) (P2NA) with methyl methacrylate and styrene successfully yielded poly(2-naphthyl acrylate)-b-poly(methyl methacrylate) and poly(2-naphthyl acrylate)-b-polystyrene block polymers, respectively, with narrow polydispersities. The P2NA obtained by RAFT polymerization had a strong ultraviolet absorption at 270 nm, and the molecular weights had no apparent effect on the ultraviolet absorption intensities; however, the fluorescence intensity of P2NA increased as the molecular weight increased and was higher than that of 2NA. (c) 2005 Wiley Periodicals, Inc.