The living radical polymerization of methyl methacrylate and styrene was successfully carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS)/ferric tri(diethyldithiocarbamate) as a novel reverse atom transfer radical polymerization initiation system in which DCDPS was a hexa-substituted ethane-type thermal iniferter, DC was a diethyldithiocarbamate group, and no additional ligands such as nitrogen- or phosphine-based compounds were required, The bulk polymerization of methyl methacrylate was carried out at 95 degreesC, and that of styrene was carried out at 120 degreesC. Poly(methyl methacrylate) and polystyrene (PSt) with high molecular weights and quite narrow molecular weight distributions (as low as 1.09 for PSt) were obtained. H-1 NMR spectroscopy revealed the presence of an alpha-(carbethoxycyanophenyl)methyl group from the initiator and an omega -DC group from the catalyst in the obtained polymers. Various chain-extension reactions under UV light or thermal treatments were successfully conducted to prove the presence and efficient reinitiating of the omega -DC group.