Potential applications (catalysis, gas sorption, etc.) of metal-organic frameworks (MOFs) incorporating secondary-building units (SBUs) stimulate the intensive search for novel ligand systems as important multifunctional bridges. Adamantane is a unique molecular platform for the construction of a variety of rigid ligands with regular geometry (angular, trigonal or tetrahedral) (see Scheme) containing azole functions. The 4-substituted 1,2,4- triazoles (tr) possess many attractive attributes: on one hand, a particular feature to form short bridges between adjacent metal ions, on the other, chemical robustness and stability.figureIn the present series of coordination polymers, N1 ,N2 -triazole donors support assembling bi- [M2( 2 -tr)3] and tri- [M3( 2 -tr)6] nuclear SBUs, which behave as multiconnected nodes in the frameworks. Alternatively, the simultaneous coordination of N1 ,N2 -tr and short inorganic bridges to the metal centers affords the discrete [M3(μ2-OH)2( 2 -tr)2] or [M3(μ3-OH)( 2 -tr)3] and polymeric [M2(μ2-X)( 2 -tr)2]n (X = Cl, NCS, SO4 2- ) units, integrated into the MOFs, that is a prerequisite of interesting properties of resulting materials. While investigating the coordination possibility of the ligand family to form metalorganic polymers, we observed that the CuII/tr/H2O system is remarkably sensitive to reaction conditions (pH value, counter anion, temperature etc.) leading to various products. Thus, in a hydrothermal reaction of CuSO4 and the angular bitopic tr2ad (adamantane-1,3-bis(triazole-4- yl)), three types of complexes containing diverse structural motifs were obtained. The first one, [Cu{tr2ad}(SO4)]·3H2O, represents the organization of metal ions into columns by means of cooperative interactions of two  2 -tr and 2-(O,O’) SO4-anions, while the organic linkers connect them in the 2D net. In case of more acidic pH, two other complexes ([Cu3{tr2ad}4(SO4)2(H2O)2]SO4·28H2O and [Cu3(tr2ad)4(SO4)(H2O)3](SO4)2· 34H2O) having isomeric networks (2D square net and porous 3D α-Po topology) based on the trinuclear linear clusters were synthesized. Our research demonstrates the potential of triazole-ligands based on adamantane scaffold in the construction of frameworks according to its extraordinary regular geometry and strictly fixed coordination directions.