Synthesis of poly(epichlorohydrin-g-4-vinylbenzyl-g-methyl methacrylate) [poly(ECH-g-VB-g-MMA)] graft copolymer was carried out by cationic ring-opening polymerization (ROP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and atom transfer radical polymerization (ATRP) methods. In the first stage, poly(epichlorohydrin) [PECH] was synthesized using epichlorohydrin monomer by ROP. In the second stage, macro-RAFT agent was synthesized by a chemical reaction of PECH with potassium ethyl xanthogenate. In the third stage, macro-RAFT agent and 4-vinylbenzyl chloride were used to obtain poly(ECH-g-VBC) graft copolymer by RAFT polymerization. In the last stage, in the ATRP of the methyl methacrylate, chloromethyl groups of the poly4-vinylbenzyl chloride segment of poly(ECH-g-VBC) graft copolymer were used as the starting functional group, poly(ECH-g-VB-g-MMA) graft copolymer with low dispersity was obtained as a result of the polymerization. The product characterization was fulfilled using spectroscopic and thermal analysis techniques such as H-1-NMR, FT-IR, TGA, SEM and GPC instruments.