An investigation of the photophysics of two complexes, [Pt((t)Bu(3)tpy)(C C-perylene)]BF4 (1) and Pt((t)Bu(2)bpy)(C C-perylene)(2) (2), where (t)Bu(3)tpy is 4,4',4 ''-tri(tert-butyl)-2,2':6',2 ''-terpyridine, (t)Bu(2)bpy is 4,4'-di(tert-butyl)-2,2'-bipyridine, and C C-perylene is 3-ethynylperylene, reveals that they both exhibit perylene-centered ligand localized excited triplet states ((IL)-I-3) upon excitation with visible light. These complexes do not display any significant photoluminescence at room temperature but readily sensitize O-1(2) in aerated CH2Cl2 solutions, as evidenced by-its characteristic emission near 1270 nm. The transient absorption difference spectra were compared to bi- and tridentate phosphine peryleneacetylides intended to model the (IL)-I-3 peryleneacetylide excited states in addition to the related phenylacetylide-bearing polyimine analogues, with the latter model being the respective triplet charge-transfer ((CT)-C-3) excited states. The transient difference spectra of the two title compounds display excited-state absorptions largely attributable to perylene localized (IL)-I-3 states yet exhibit somewhat attenuated excited-state lifetimes relative to those of the phosphine model chromophores. The abbreviated lifetimes in 1 and 2 may suggest the involvement of the energetically proximate (CT)-C-3 triplet state exerting an influence on excited-state decay, and the effect appears to be stronger in 1 relative to 2, consistent with the energies of their respective (CT)-C-3 states.