Two Co(III) complexes [Co(L1)2]BF4·H2O (1) and [Co(L2)(N3)3] (2) with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1) and the condensation product of 2-acetylpyridine and Girard’s P reagent (HL2Cl) and Co(BF4)2·6H2O have been synthesized. Complexes were characterized by elemental analysis, IR and NMR spectroscopy and X-ray crystallographic analysis. DFT calculations revealed the thermodynamical stability of obtained complexes.