- The tripodal “click” compound, tris(4-trimethylsilylmethyl-1,2,3-triazolylmethyl)amine (TTTA), was prepared and investigated as a ligand for copper-catalyzed single electron transfer-living radical polymerization (SET-LRP) of methyl methacrylate (MMA). Bulk polymerizations catalyzed by Cu0/CuBr2/TTTA with the molar ratio of [MMA]0/[EBiB]0/[CuBr2]0/[TTTA]0 = 200/2/1/1 and a 1.0x1.0 cm2 Cu0 sheet afforded fast and well-controlled polymerization (76% conversion with Mw/Mn = 1.19 after 3.5 h). Higher amounts of added air generally gave slower polymerizations although the Mw/Mn values remained narrow (<1.3) even when the polymerization was carried out under aerobic conditions. Decreasing initial concentrations of the catalyst system Cu0/CuBr2/TTTA or polymerization temperatures also resulted in slower polymerizations and yielded polymers with broader dispersity. Kinetic studies at the temperature range of 40–90 oC revealed the apparent activation energy (Ea) of 22.6 kJ/mol