Abstract: A new Co(Ⅱ) coordination compound, namely, CoL₄Cl₂ is synthesized and its thermochemical properties is characterized. The specific molar heat capacity (C_{p, m}) of CoL₄Cl₂ from 283.15 K to 353.15 K is determined by micro-calorimeter and calculated by density function theoretical (DFT) calculations. The theoretical thermodynamic properties of H_T-H_{298.15 K} and S_T-S_298.15K are also studied. Moreover, the thermochemical behavior of the dissolution of CoL₄Cl₂ in N, N-dimethyl formamide (DMF) is measured using a DC08 Calvet microcalorimeter at 298.15 K. The results show that the dissolution is an endothermic process, and the enthalpy of dissolution in DMF is 45.61±0.77 kJ/mol at 298.15 K.