A new process for the synthesis of high-vinyl (50-70% 1.2-units) butadiene polymers and copolymers on the basis of hydrocarbon-soluble organosodium catalyst is proposed. The catalyst can be readily synthesized in aliphatic solvents from commercially available starting materials; the equipment common for the synthesis of organolithiums is suitable. Main parametres of butadiene polymerization and styrene-butadiene copolymerization including kinetics, molecular weights and monomer reactivity ratios for copolymerization were investigated. The synthesis of polystyrene, 3.4-polyisoprene, styrene-butadiene block-copolymers, nonfunctional butadiene and styrene-butadiene liquid rubbers, and other high-vinyl polymers is also possible.