Living/controlled radical polymerization of methyl methacrylate (MMA) was investigated using a new initiating system, i.e. DCDPS/FeCl3/PPh3, in which diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS) is a hexa-substituted ethane thermal iniferter. The polymerization mechanism belongs to a reverse ATRP process. The polymerization was closely controlled in bull; and in solution at quite low temperature such as 75 or 60 degrees C. The molecular weights of so-obtained PMMA were high and polydispersities were quite narrow (M-w/M-n = 1.20-1.31). End group analysis result using H-1 NMR spectroscopy shows that the polymer obtained is omega-functionalized by a chlorine atom. With the Cl atom at the chain end, PMMA obtained could be used as macroinitiator to proceed chain-extension reaction with MMA and block copolymerization reaction with styrene in the presence of CuCl/bipy catalyst via a conventional ATRP process.