Synthesis of poly(methyl methacrylate-block-ethylene glycol-block-methyl methacrylate) triblock copolymers by reversible addition–fragmentation chain transfer (RAFT) by using a novel dual macro initiator (RAFT-agent) is reported. RAFT-agent is obtained from potassium salt of the ethyl xanthegonate and the terminally brominated poly(ethylene glycol) (Br-PEG-Br) which is synthesized by the reaction of poly(ethylene glycol) [PEG] with Mn= 3000 Dalton and 3-bromopropionyl chloride. The principal parameters such as monomer concentration, initiator concentration, and polymerization time that affect the polymerization reaction are evaluated. The characterization of the products is achieved using Fourier-transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H-NMR), gel-permeation chromatography (GPC), thermogravimetric analysis (TGA), and fractional precipitation (γ) techniques. Molecular weights of the polymers obtained from GPC agreed with the theoretical values. RAFT polymerization is used to control the polymerization of MMA over a broad range of molecular weights.