The pyridine-2-carboximidates (R = methyl (1a), ethyl (1b), isopropyl (1c), cyclopentyl (1d), cyclohexyl (1e), n-octyl (1f), benzyl (1g)) have been prepared from the reaction of 2-cyanopyridine with the corresponding alcohols. The cyclopentyl-substituted 1d was found to be highly effective ligand for copper-catalyzed ATRP polymerization of methyl methacrylate (MMA). The effects of solvents, temperature, catalyst/initiator, and solvent/monomer ratio on ATRP of MMA have been studied systematically for the CuBr/2d catalytic system. The optimum condition of the ATRP of MMA was found to be[CuBr]_o/[1d]_o/[EB1B]_o/[MMA]_o=1 : 2 : 1 : 400 at 60 ℃ in veratrole solution, which yielded well-defined PMMA with a narrow molecular weight distribution of 1.14.