In this work a laboratory polymerization scale process was studied for the production of polybutadiene with high content of cis-1,4 repeating units. A Ziegler–Natta catalytic system based on neodymium versatate (catalyst), diisobutylaluminium hydride (cocatalyst) and tert-butyl chloride (chlorinating agent) was used. The influence of solvent nature (pure grade) and possible contaminants (electron donors) in a recovered solvent from a butadiene–styrene anionic polymerization industrial plant on the stereoselectivity and catalytic activity, molecular weight and molecular weight distribution of the resultant polybutadienes was studied. The polymers were characterized by infrared spectroscopy and size exclusion chromatography. Polybutadienes with cis-1,4 units content in the range of 99–98% were produced. The polymers weight-average molecular weight, Mw, varied from 2.23×105 to 4.47×105 and the molecular weight distribution, MWD, from 3.1 to 5.1.