Abstract: By using a method of anionic polymerization, the micro-structure of polybutadiene was studied for naphthalene lithium and butyl lithium as initiators, extracted naphtha and cyclohexane as solvents, and THF as a polar additive. According to experimental data, the following mechanism of polymerization was proposed: CH2CH=CHCH2Li Based on the kinetics of the chemical reactions and the theory of total probability, a quantitative relation between the content of the 1, 2-struc-ture in the product(Bv) and the concentration of the tetrahydrofuran was deduced: where From literature data including Et2O as well as tetrahydrofuran as the polar additive, the above equation has been generalized to: where: P. A. is the concentration of the additive.