A novel benzodithioate compound with an anthracene structure (anthracen-9-ylmethyl benzodithioate, AMB) was synthesized. Using AMB as the chain transfer agent, the RAFT polymerizations of styrene with AIBN as an initiator were carried out in difference reaction conditions. The polymerization results showed that AMB was an effective RAFT agent for the RAFT polymerizations of styrene with the characteristics of "living"/controlled free radical polymerization. The structure of the obtained polymers was characterized by H-1 NMR. The results showed that the polymers contained an anthrancene moiety of AMB in the end and showed enhanced fluorescence property than AMB in DMF solution. The chain extension experiments of the obtained polymer with two different monomers (styrene and methyl acrylate) were successfully carried out.