A comprehensive study of a series of four monodisperse, metal-organic T-conjugated oligomers of varying length is reported. The oligomers are based on the aryleneethynylene architecture, and they contain a 2,2 ' -bipyridine-5,5 ' -diyl (bpy) metal binding unit. The photophysical properties of the free oligomers and their complexes with the (L)Re-I(CO)(3)X chromophore (where L = the bpy-oligomer and X = Cl or NCCH3) were explored by a variety of methods including electrochemistry, UV-visible absorption, variable temperature photoluminescence (PL), transient absorption (TA), and time-resolved electron paramagnetic spectroscopy (TREPR). The absorption of the free oligomers and the metal complexes is dominated by the pi,pi* transitions of the pi -conjugated oligomers. The free oligomers feature a strong blue fluorescence that is quenched entirely in the (L)Re-I(CO)3X complexes. The metal-oligomers feature a weak, relatively long-lived red photoluminescence that is assigned to emission from both the 3 pi,pi* manifold of the pi -conjugated system and the d pi Re --> pi* bpy-oligomer metal-to-ligand charge transfer ((MLCT)-M-3) state. On the basis of a detailed analysis of the PL, TA, and TREPR results an excited-state model is developed which indicates that the oligomer-based (3)pi,pi* state and the (MLCT)-M-3 states are in close energetic proximity. Consequently the photophysical properties reflect a composite of the properties of the two excited-state manifolds.