The present work aims chiefly to study the thermal behaviour of complex compounds with general formula: [M(HL)xH2O](A)yH2O (where HL=C13H11N4O2=6-(2-pyridylazo)-3-acetamidophenol (PAAP), M=Cu(II), Zn(II), Cd(II) and Fe(III) x=1, 3; y=2, 5) while A=CH3COO– (Ac), Cl2. The second formula is [M(H2L)xH2O]Cl2yH2O, (where H2L=C13H12N4O2 (PAAP), M=Ni(II), Co(II) x=3; y=4, 6). The compounds were identified by elemental analysis, FT-IR spectra and TG/DTG,DTA methods. It was found that during the thermal decomposition of complex compounds water molecules of crystallization are released in the first step. In the next step the pyrolysis of organic ligand takes place. Metal oxide remained as a solid product of the thermal decomposition. Mass spectroscopy has been used for the determination of the thermal decomposition on the intermediate products. It was found that the thermal stability of the studied compounds increases as the ionic radii decreases. The activation energy E, the entropy change S*, the enthalpy H* change and Gibbs free energy change G* were calculated from TG curve.