Novel ligands, alkyl (R = methyl (1a), isopropyl (1b), cryclopentyl (1c), cyclohexyl (1d)) pyridine-2-carboximidates, have been prepared by the reaction of 2-cyanopyridine with the corresponding alcochols. While all these ligands with CuBr showed the polymerization activity of methyl methacrylate, the CuBr/2(1c) catalytic system was very effective in our previous work. Using our new catalytic ligand system, the polymerization of 1,3-butadiene (BD) was carried out successfully. Several effects, such as ligand, solvent, temperature and kinetic study of homopolymerization of 1,3-butadiene have been studied systematically.