The photophysical properties of [Ru-bidppz-Ru](4+), [Os-bidppz-Os](4+), and the bridging ligand bidppz (bidppz = 1,1'-dipyrido[3,2-a:2',3'-c]phenazin-1,1'-yldipyrido[3,2-a:2',3'-c]phenazine) are investigated. Time-resolved spectroscopic studies were performed on (sub)pico- to microsecond time scales, offering insight into the excited states responsible for the photophysical behavior of the two complexes in different solvents. In particular, [Ru-bidppz-Ru](4+) shows a long excited-state lifetime, 9.7 mus, in deaerated dichloromethane solution, that becomes much shorter (360 ns) in deaerated butyronitrile. The solvent plays a crucial role for the spectroscopic properties of this complex, since the energy of the triplet metal-to-ligand charge-transfer ((MLCT)-M-3) excited state is influenced by the polarity of the medium. (Sub)picosecond transient absorption spectra in dichloromethane indicate thermal population of the long-lived triplet intraligand ((IL)-I-3) state of the bridging ligand from the lower lying (MLCT)-M-3 state. For [Os-bidppz-Os](4+) in dichloromethane the (MLCT)-M-3 state lies lower in energy and no interaction of this state with the (IL)-I-3 state of the bridging ligand is observed.