Living" radical polymerization of methyl methacrylate was investigated using a new initiating system, i.e. DCDPS/FeCl 3/PPh 3, in which diethyl 2,3 dicyano 2,3 diphenyl succinate(DCDPS) is a hexa substituted ethane thermal iniferter. The polymerization mechanism belongs to a reverse ATRP process. The polymerization was closely controlled in bulk at 75 ℃, polymethyl methacrylate(PMMA) with a high molecular weight and quite narrow polydispersity ( M w/ M n=1 20—1 29) was obtained. End group analysis by 1H NMR spectroscopy shows that the resulting PMMA is ω functionalized by a chlorine atom, which is also confirmed by the chain extension reaction in the presence of CuCl/bipy catalyst via a conventional ATRP process. [WT5HZ]