A new selenium-based reversible addition-fragmentation chain transfer (RAFT) agent, 4-cyanopentanoic acid diselenobenzoate (RAFT-Se), was synthesized and utilized in the surface-initiated RAFT polymerization of 4-vinylpyridine (4VP) on silicon substrate. The results indicate that the RAFT-Se can control the surface-initiated RAFT polymerization, as evidenced by the number-average molecular weight that increase linearly with monomer conversion, molecular weights that agreed well with the predicted values, and the relatively low polydispersity indexes. The surface-initiated RAFT polymerization with the RAFT-Se was the same polymerization mechanism as its analog, 4-cyanopentanoic acid dithiobenzoate (RAFT-S). The grafting density of the poly(4-vinylpyridine) brushes prepared in the presence of RAFT-Se (sigma(RAFT-Se)) and RAFT-S (sigma(RAFT-S)) was estimated to be about 0.51 and 0.66 chains/nm(2), respectively. In addition, the end of polymer chains on silicon substrate contains selenium element which may be useful in biosensor applications. (c) 2013 Elsevier Ltd. All rights reserved.