Novel ligands, alkyl pyridine-2-carboximidate (R 〓 methyl (1a), isopropyl (1b), cyclopentyl (1c), cyclohexyl (1d)) have been prepared by the reaction of 2-cyanopyridine with the corresponding alcohols. While all these ligands with CuBr showed the polymerization activity, the CuBr/2(1b) and CuBr/2(1c) catalytic systems were effective on the copolymerization of methyl methacrylate(MMA) and isobutylene(IB) especially compared to other ligands such as dHbpy(1e), PMDETA(1f), and TREN-Me_(6)(1g), which are the good ligands. Using the CuBr/2(1c) catalytic system, several effects, such as ligand, solvent, temperature and initiator on ATRP of copolymerization have been studied systematically. Pseudo-first order plot of ln［M］_(o)/［M］vs. time gave the linearity, and the molecular weight increased with increasing monomer conversion.