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 alcochols. 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-Me₆ (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.