A novel terpyridine ligand containing a pentaphenylphenyl moiety linked to the terpyridyl core (1-terpyridyl-2,3,4,5,6-pentaphenyl-benzene (TPPPB)) has been synthesized in good yield and reacted with Pt(DMSO)2Cl2, to produce the cationic complex Pt(TPPPB)ClCl (5). 5 was studied structurally and spectroscopically. It is observed to be brightly luminescent in the solid state at room temperature and at 77 K, with no change in λem max. The complex exhibits reversible vapochromic behavior upon exposure to methylene chloride vapors, changing color from red (5-R) to green (5-G). The shift to higher energy in the emission maximum from 654 to 514 nm is the largest vapochromic shift (140 nm) yet reported. The Pt(TPPPB)ClCl complex exhibits high selectivity for certain volatile organic compounds (VOCs) including methylene chloride, ethanol, ethyl acetate, and acetonitrile. The crystal structures of both the green and red forms have been determined by single-crystal X-ray diffraction. In both forms, the cationic Pt(II) complex possesses the anticipated square-planar coordination geometry that is distorted as a consequence of constraints from the terpyridyl binding. Analysis of the crystal packing of the green form (5-G) reveals the presence of non-interacting Pt···Pt separations with distances of 3.9092(9) and 4.5483(11) Å and a zigzag arrangement between neighboring Pt(II) ions. The red form (5-R) contains complexes that are stacked with Pt···Pt separations of 3.2981(14) and 3.3427(14) Å, indicative of metallophilic interaction. The change in the emitting state, as a consequence of the effect of the volatile organic compounds, results from a disruption of the d8−d8 metallophilic interactions in the red form and its metal−metal-to-ligand charge transfer (MMLCT) excited state to a more-localized Pt(dπ)-to-tpy(π*) metal-to-ligand charge transfer (MLCT) excited state in the green form.