The designed construction of metal−organic frameworks (MOFs) has been of intense interest, due to their topological features and intriguing aesthetic structures, as well as their promising applications in molecular sorption, heterogeneous catalysis, molecular magnetism, drug delivery, and so on. Most recently, MOFs attracts considerable attention as safe materials for adsorptive hydrogen storage because of their exceptionally high specific surface areas and chemically tunable structures. Our recent study has been mainly focused on the syntheses and construction of new MOFs from accessible multicarboxylic acids and imidazole-based spacers. In order to investigate the sorption properties of the MOFs by varying the metal centers incorporated in the structures, the rigide and conjugated molecules 1,2,4,5-benzenetetracarboxylic acid (1,2,4,5-BTC) and 4,4’-bis(1-imidazolyl)biphenyl (BIBPh) were chosen as the starting materials together with different divalent 3d-metal ions. Utilizing solvothermal technique, three new MOFs, [M2(BIBPh)2(1,2,4,5-BTC)]n (where M = Co (1), Ni (2), Zn (3)) have been obtained. The composition and structure of tridimensional polymeric complexes were demonstrated by various methods of analyses (EA, IR, thermogravimetry, single crystal X-ray). Thermogravimetric study has demonstrated an exceptional thermal stability of polymeric samples up to >350 °C when a process of irreversible destruction of molecular carcass is occuring. Single crystal X-ray structure investigation of coordination compound 1-3 has demonstrated, that in the crystalline phase a 3D polymeric structure was obtained, where metal ions are interconnected by bridging molecules of hexadentate ligand 1,2,4,5-BTC and bidentate melecules of BIBPh. In polymers are present large cavities where solvent molecules of H2O are adsorbed. Sorption properties of the synthesized compounds will be also discussed. Crystal structure of the polymeric compound [Co2(BIBPh)2(1,2,4,5-BTC)]n.