Here we synthesized the highly porous rht-MOF-9 as the first example of an rht-MOF having a polycyclic central core. This material was synthesized from a predesigned polyheterocyclic nitrogen-rich hexacarboxylate (tri-isophthalate) ligand, which serves as the 3-connected, trigonal molecular building block (MBB). When reacted under the proper conditions, this ligand, having three coplanar isophthalic acid moieties, codes for the in situ formation of the targeted 24-connected copper-based supermolecular building block (SBB) having rhombicuboctahedral geometry. This combination of a 24-connected building block linked through 3-connected nodes results in a novel material with the singular rht topology. The rht-MOF-9 compound exhibits promising H2 and CO2 adsorption properties in comparison to previously reported rht-MOFs. © 2014 American Chemical Society.