Butadiene rubbers are frequently produced through solution polymerizations using Ziegler–Natta catalysts based on neodymium. Particularly, there is great interest in developing rubbers that present enhanced processability during the formulation step. For this reason, the present work investigated the production of butadiene rubbers in the presence of polar additives, such as methyl methacrylate, methacrylic acid, and water, through solution polymerizations, using neodymium versatate as catalyst. The obtained results confirmed the possibility of producing butadiene rubbers with polar character that presented improved processability properties during the vulcanization stage. In addition, a new use for water and the manufacture of copolymers of butadiene and oxygenated monomers in polymerization processes that make use of neodymium catalysts are reported for the first time.