Alkyl pyridine-2-carboximidate [R = isopropyl (1a), cyclopentyl (1b), cyclohexyl (1c), methyl (1d)] ligands were successfully prepared in one step for their application in atom transfer radical polymerizations (ATRP). While BD could be polymerized successfully in our CuBr/alkyl pyridine-2-carboximidate catalytic systems, other ligands, such as 4,4-di-n-heptyl-2,2-bipyridine (dHbpy), N,N,N′,N′,N″-pentamethyldiethylenediamine (PMDETA), and tris(2-(dimethylamino)ethyl)amine (TREN-Me6), which are good ligands for the polymerization of styrene and/or methyl acrylate, showed no or little activity in the polymerization of BD. Though its polymerization rate was slow and its conversion minimal, this result might be the first example of the polymerization of BD using ATRP. The effects that the ligand, solvent, temperature, initiator concentration, solvent/monomer ratio, and catalyst/monomer ratio have on the ATRP of BD using CuBr/alkyl pyridine-2-carboximidate were studied systematically. The optimum conditions for the ATRP of BD were found to employ [CuBr]0/[1a]0/[PEBr] 0/[BD]0 at a 1:2:1:100 ratio at 80 °C in a veratrole solution (w/w = 1:2); these conditions yielded a well-defined polybutadiene (PBD) having a narrow molecular weight distribution of 1.41.