This study addresses, in detail, the orbital nature and the extent of metal-metal communication in the lowest emitting triplet state of Re-4(CO)(12)(4,4'-bpy)(4)Cl-4 (where 4,4'-bpy = 4,4'-bipyridine) as well as the symmetry of the lowest (MLCT)-M-3 manifold in comparison to that of the ground state. All spectral evidence points to (1) a (MLCT)-M-3 excited manifold localized between a single Re(l) corner and an adjacent bridging ligand, (2) a transient mixed-valence state that is completely localized between a single transiently oxidized Re center and the adjacent metals, and (3) a second-order charge transfer from a localized transiently reduced bridging ligand to the adjacent Re(I) center to which it is attached, effectively lowering its oxidation state. The orbital nature of the lowest (MLCT)-M-3 manifold is fully corroborated by a molecular orbital diagram derived from quantum chemical modeling studies, while the existence of the localization, localized mixed valency, and second-order charge transfer rely on spectral evidence alone. This work makes use of low-temperature time-resolved infrared (TRIR) techniques as well as a luminescence study. Many of the nuances of the luminescence and TRIR data interpretation are extracted from statistical analysis and quantum chemical modeling studies. The relative concentrations of the dominant conformers that exist for Re-4(CO)(12)(4,4'-bpy)(4)Cl-4 have also been estimated from Boltzmann statistics.