The coordination-driven self-assembly of supramolecular hexagonal prisms has been achieved upon mixing a hexakis[4-(4-pyridyl)phenyl]benzene donor ligand and carboxylate donor ligands such as sodium terephthalate, sodium (1,1'-biphenyl)-4,4'-dicarboxylate, sodium 4,4'-(diazene-1,2-diyl)dibenzoate, and 4,4'-dipyridyl with cis-Pt(PEt(3))(2)(OTf)(2) in a 1:3:6 ratio. Four assembled hexagonal prisms have been characterized by (31)P and (1)H NMR multinuclear spectroscopy as well as electrospray ionization mass spectrometry. Molecular force-field simulations provide the possible conformation and size of each structure.