The design and synthesis of coordinative truncated tetrahedra is described. The coordination-driven self-assembly of a truncated tetrahedron was achieved using 90 degrees organoplatinum acceptors and a hexapyridyl ligand with six-fold symmetry under mild conditions. This tetrahedron can act as a host toward 1,3,5-triphenylbenzene. The truncated tetrahedral structures and the host-guest complex were identified using multinuclear (P-31 and H-1) NMR spectroscopy, electrospray ionization mass spectrometry, X-ray crystallography, and pulsed-field-gradient spin-echo NMR, along with computational simulations.