RAFT polymerization and surface-initiated RAFT polymerization (SI-RAFT) of chloroprene was studied. The SI-RAFT polymerization rate of chloroprene was found to be slower than free solution RAFT polymerization, and further regulated by the graft density of grafted polymers. The resulting polychloroprene-grafted silica nanoparticles were directly crosslinked to obtain matrix-free poly-chloroprene nanocomposites that showed good nanoparticle dispersion and superior mechanical properties compared with unfilled polychloroprene rubber. (C) 2017 Elsevier Ltd. All rights reserved.