Luminescent metal-organic frameworks (MOFs) continue to attract close consideration of scientists in virtue of their expanding applications, such as chemical, biological and radiation detection, medical imaging and electro-optical devices [1]. We have recently reported on the synthesis and X-ray characterization of such kind of coordination networks [2]. Here we present the results of our study on characterization of some bi- and polynuclear zinc and cadmium coordination compounds supported by 1,2-cyclohexanedionedioxime (NioxH2) and bridging bidentate ligands: 4,4'-bipyridyl (bpy), 1,2-bis(4-pyridyl) ethane (bpe), 1,3-bis(4-pyridyl) propane (bpp), dipiridil sulfide (dps) and adipic acid (H2adi) by thermogravimetric analysis. Investigation of the thermal behaviour of complexes is important for appreciation of the stability of crystal lattice for their possible application as porous materials, e.g. for gas storage and separation. Considering the potential use in catalysis of these compounds, knowledge of their thermal stability is also strictly necessary, since catalytic technological processes often occur at high temperatures. Thermogravimetric measurements were performed on a 1500D derivatograph (MOM, Hungary) in the air atmosphere under non-isothermal conditions over the temperature range of 20–1000oC. The studied compounds showed individual behaviour upon heating, the thermal degradation started depending on the ligand nature and, to a lesser extent, on the metal. All compounds showed thermal stability up to 120 °C, but with rising of temperature, compounds containing carboxylic acids residues began to suffer thermal degradation by decarboxylation and rearrangement of the newly formed product. Compounds presenting a more pronounced thermal stability will be further studied under catalytic processes.