A series of cobalt(II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes (tridentate [NOO] ligands) was prepared and characterized by FT-IR and elemental analysis along with single-crystal X-ray diffraction. The X-ray diffraction analysis revealed that a dinuclear centrosymmetrical structure formed, in which each cobalt atom is surrounded by two bridged ligands and two acetate groups as a distorted octahedron. These dinuclear cobalt complexes displayed high catalytic activities for the polymerization of 1,3-butdiene on activation with organoaluminum cocatalysts to yield cis-1,4-polybutadiene with high selectivity. Ethylaluminum sesquichloride (EASC) was found to be the most efficient cocatalyst resulting in high conversion of butadiene and cis-1,4 content in the polymers with moderate molecular weight. The high catalytic activity and stereoselectivity could be achieved in a wide range of reaction conditions. All the dinuclear cobalt complexes (C1-C6) yielded predominantly cis-1,4-polybutadienes (> 96%) with negligible amounts of trans-1,4 (< 2.4%) and 1,2-vinyl (< 1.5%) products under the Al/Co molar ratio of 80 at 25 °C. The ligand modification by varying the substituents at the 4-position of phenol and on the imino-N aryl ring showed slight influence on the catalytic activity and microstructure of the resulting polymers.