A series of ruthenium(II) complexes coordinated to the bridging ligand dipyrido(2,3- a;2′,3′- h)phenazine (dpop) has been prepared and the spectroscopic, electrochemical, photochemical and intervalence properties studied. The mono and bimetallic [((NH 3) 4Ru) n (dpop)] 2 n+ ( n = 1, 2) ions display lowest energy MLCT transitions at 629 (ϵ = 7.3 × 10 3 M −1 cm −1) and 755 (ϵ = 18 × 10 3 M −1 cm −1) nm, respectively, in CH 3CN, with higher energy MLCT and IL transitions. The Ru 2+/3+ centered couples are more positive than those reported for similar bis-bipyridylruthenium(II) dpop complexes, and the bimetallic [((NH 3) 4Ru) 2(dpop)] 5+ mixed valence ion displays an IT absorption band at 1670 nm (ϵ = 1250 M −1 cm −1) in D 2O. The [(dpop) 3Ru] 2+ ion has a lowest energy MLCT transition at 512 nm (ϵ = 22 × 10 3 M −1 cm −1) in CH 3CN, and displays an emission maximum at 710 nm with oxygen sensitive intensity. Irradiation of the [(dpop) 3Ru] 2+ ion at 546 nm in de-oxygenated CH 3CN produces the release of a dpop ligand with Φ = 6 × 10 −4 mol/E.