Metal–organic materials (MOMs) represent an emerging class of materials that have attracted the imagination due to highly functional character and significant contributions in numerous applications areas including, but not limited to, catalysis, sensors, separations, transport of hydrogen, and drug delivery. MOMs are comprised of metal moieties and organic ligands and are exemplified by a diverse group of discrete (e.g. metal–organic clusters) or polymeric structures (e.g. coordination polymers or metal–organic frameworks (MOFs)). Polymeric MOMs demonstrate how crystal engineering holds great promise for control of the arrangement of atoms in space due to the ability to target specific molecular building block (MBB) with given geometry and directionality prior to the assembly process as well their inherent modularity and prototypal for a diverse range of structures. Recently more attention has been paid to the multinuclear metal-clusters as supermolecular building blocks (SBBs), which can be used as nodes with enhanced variety of coordination algorithms and size compare with a single metal ion and give rise to a family of cluster-based polymers. Apart from design perspective, multinuclear clusters may introduce their inherent extraordinary physical properties to the polymeric structure. The cluster-based polymers may be assembled from pre-designed and pre-synthesized SBBs. In the report will be demonstrated how the tri-, and hexanuclear metal carboxylate clusters linked by spacer organic ligands, lead to porous polymeric MOMs. The versatile polymeric architecture has been achieved with μ3-oxo trinuclear homo- and heterometalic type clusters. In combination with spacer ligands the 1D chains, 2D sheets polymers as well as a 3D highly porous MOM (Fig.1) with a large total potential solvent area of 44.1% of unit cell volume have been obtained. The 1D and 2D polymers have been also constructed from nanoscale hexanuclear manganese carboxylate clusters featuring the {MnII4MnIII2(μ4-O)2} core with different spacer ligands. Some of them revealed the porous structure. The discrete binuclear Co(III) bis-dioximates with wheel-and–axle topology may also afford porous supramolecular MOM (Fig.2) with hourglass-like channels of diameter ca 0.6  1.3 nm and solvent area of 19.6% of unit cell.figure