Due to the use of coal fuel, CO₂ has been steadily increased in nature. Global warming due to the accumulation of carbon dioxide has led our attention to conversion CO₂ to industrial materials. One of the efficient methods is synthesis of cyclic- or poly- carbonate through ring opening reaction of propylene oxide with homogeneous catalyst. Co complexes containing SALEN(N,N’-bis(salicylidene)ethylenediamine) ligand have been reported effective catalyst in the reaction. A recent research trend is to use only catalyst without co-catalyst such as DMAP{4-dimethylamonopyridine} and tetraalkylamoniumiodide in the ring opening reaction. Following this trend we have focused on ligands with cationic moieties that can replace co-catalysts. In this study, the new cobalt complex containing SALEN ligand with pyridine was synthesized for developing new Co(Ⅲ) system used in transformation of carbon dioxide. A new cobalt(Ⅲ) complex of pyridoxyl SALEN ligand was synthesized by the reaction of pyr2en ligands (pyr2en =(N,N ‘-bis(pyridoxylideneiminato)ethylene) ) with Co(OAc)₂. The complex was characterized by various spectroscopic methods such as infrared spectroscopy, high resolution mass analysis, and single crystal X-ray crystallography. The tetradentate Schiff base ligand binds cobalt metal in a plane and forms an octahedral geometry by coordinating acetate and DMSO. The synthesized cobalt complex was used in the cycloaddition reaction of CO₂ to propylene oxide and the detailed study will be presented.