One-step synthesis of block-graft copolymers by reversible addition-fragmentation chain transfer (RAFT) and ring-opening polymerization (ROP) by using a novel initiator was reported. Block-graft copolymers were synthesized in one-step by simultaneous RAFT polymerization of n-butylmethacrylate (nBMA) and ROP of epsilon-caprolacton (CL) in the presence of a novel macroinitiator (RAFT-ROP agent). For this purpose, first epichlorohydrin (EPCH) was polymerized by using H2SO4 via cationic ring-opening mechanism. And then a novel RAFT-ROP agent was synthesized by the reaction of potassium ethyl xanthogenate and polyepichlorohydrin (poly-EPCH). By using the RAFT-ROP agent, poly[CL-b-EPCH-b-CL-(g-nBMA)] block-graft copolymers were synthesized. The principal parameters such as monomer concentration, initiator concentration, and polymerization time that affect the one-step polymerization reaction were evaluated. The block lengths of the block-graft copolymers were calculated by using 1H-nuclear magnetic resonance (1H NMR) spectrum. The block length could be adjusted by varying the monomer and initiator concentrations. The characterization of the products was achieved using 1H NMR, Fourier-transform infrared spectroscopy, gel-permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, elemental analysis, and fractional precipitation () techniques. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 26512659