As part of an effort to develop new lumaphors involving late transition metal ions, this report describes the synthesis and characterization of the first platinum(II) derivatives containing 2,2′:6′,2″-terpyridine (trpy) and cyanide as co-ligands. According to existing models, including cyanide in the coordination sphere should raise the energies and minimize the influence of short-lived d–d excited states that otherwise compromise the excited-state lifetime. Both [Pt(trpy)(CN)]⁺ and the 4′-cyano-2,2′:6′,2″-terpyridine analogue [Pt(CN–T)(CN)]⁺ are emissive in dichloromethane solution, but the signals are weak. Part of the problem is that the d–π* charge-transfer excited states also rise in energy, so that the emission actually originates from a ³π−π* state with a relatively low radiative rate constant. However, another member of the series, the 4′-dimethylamino-2,2′:6′,2″-terpyridine (dma–T) derivative [Pt(dma–T)(CN)]⁺, proves to be a very promising platform with an emission quantum yield of ϕ = 0.26 and an excited-state lifetime of τ = 22 µs in room-temperature, deoxygenated dichloromethane solution. In the dma–T complex the electron-rich dimethylamino substituent provides the basis for an emissive, but largely ligand-based, charge-transfer excited state. The orbital parentage is such that the photoluminescence persists in donating solvents like dimethylformamide, which ordinarily quenches d–π* excited states in complexes of this type.