Coordination polymers or metal-organic frameworks (MOFs) are a new member in the vast field of porous materials that have gained a tremendous attention in the last two decades because the voids inside the frameworks can accommodate guest molecules for a number of applications. [1] High thermal stability is important for reaching practical implementations of these compounds being a clue for good stiffness, rigidity, robustness and structural integrity estimation. Four new coordination polymers have been synthesized and characterized from room temperature to 1000 °C under flowing nitrogen atmosphere: [Co3(BIBP)2(BTC)2(H2O)2]n (1), {[Ni3(BIBP)3(BTC)2(H2O)4]·2H2O}n (2), [Zn(BIBPH)(BTC)]n (3), {[Co(BIBP)1.5(HBTB)]·H2O}n (4), where BIBP = 4,4ʹ-bis((1H-imidazol-1-yl)biphenyl, BTC = 1,2,3benzenetricarboxylate, BTB = 1,3,5-tris(4-carboxyphenyl)benzene. Thermogravimetric trace for 1, 2 and 4 allowed to identificate the number of water molecules in the internal and external sphere of the complexes. Compound 2 loses 2 water molecules (2%) from the external sphere up to 150 °C and other 4 water molecules (4%) from internal sphere between 250 and 350 °C, that is similar to compound 1 - 2 water molecules (1,5 %) from internal sphere - between 300 and 350 °C. Coordination polymer 4 decomposes into three steps observed on the DTA curve, the compound has a small weight loss of 1 % up to about 340 °C, which corresponds to the loss of water molecules from the crystalline network. One interest was to see the effect of water removal from channels within the structures - in the absence of the guest molecules the compounds are thermally stable up to 250 - 340 °C. Compound 3 is stable up to 230 °C, a sudden loss of 35 % up to 440 °C occurs, then the compound gradually decomposes. High thermal stability can make these materials eligible in technical processes involving heating.