Atom transfer radical polymerization (ATRP) is one of the most successful controlled/"living" radical polymerization. We reported a systematic study of the ATRP of methyl methacrylate (MMA) using the catalytic system comprising CuX.alkyl pyridine-2-carboximidates. Silicon groups are usually better π-electron donor/acceptor in comparison to carbon in the same group. To compare multidentate amine ligand containing silicon versus carbon, several amine ligands with silicon groups were prepared. The amine ligands containing silicon groups were found to be highly effective ligand for copper(I) bromide catalyzed ATRP of MMA. The effects of solvent, temperature, catalyst/initiator and solvent/monomer ratio on ATRP of MMA have been studied systematically. The optimum conditions for the ATRP of MMA were found to be a [CuBr]_o/[Ligand]_o/[EB₁B]_o/[MMA]_o ratio of 1 : 2 : 1 : 400 at 80℃ in a veratrole solution.