A hexa-substituted ethane type compound, diethyl-2,3-dicyano-2,3-di(p-tolyl)succinate (DCDTS), was successfully synthesized and used for initiation of methyl methacrylate (MMA) polymerization. The reaction demonstrated the characteristics of a ''living'' polymerization; i.e., both the yield and the molecular weight of the resulting polymers increased linearly with increasing reaction time, the molecular-weight distribution of PMMA obtained was similar to1.60 and almost unaffected by the conversion, and the resultant polymer can be chain extended by adding fresh MMA. End group analysis of the resultant PMMA confirmed that DCDTS behaves as a thermal iniferter for MMA polymerization. A block copolymer was prepared from the resultant PMMA, which contains a hexa-substituted C-C bond functional end group.