The synthesis, structural characterization, and photoluminescence properties of a new platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan- 2,2'-diacetylide (tda), Pt(dbbpy)( tda) [dbbpy) = 4,4'-di-tert-butyl-2,2'-bipyridine], are described. In CH2Cl2, Pt( dbbpy)( tda) exhibits a strong visible charge-transfer absorption and broad emission centered at 562 nm. The photoluminescence quantum yield and excited-state lifetime are 0.52 and 2.56 mu s, respectively, at room temperature. These parameters indicate that the planarization and rigidity introduced by the cyclic diacetylide leads to a lower-energy-absorbing species displaying enhanced photophysics relative to the analogous Pt( dbbpy)( C = CPh)(2). Time-dependent density functional theory calculations, which include solvation by CH2Cl2 via the polarizable continuum model, are used to reveal the nature of the excited states in these molecules that are responsible for the charge-transfer transitions. The 77 K emission spectra of the two compounds in EtOH/MeOH glasses are compared, uncovering tda-based ligand-localized phosphorescence in the title compound.