A ruthenium(II) polypyridine-type complex based on the dipyridophenazine ligand with a directly fused imidazole unit (LI, dipyrido[3,2-a:2',3'-c]phenazine-10,11-imidazole) has been synthesized, and its electrochemical and photophysical properties have been studied. The cyclic voltammogram of [Ru(tbbpy)(2)(L1)](2+) (C1) (tbbpy is 4,4'-tert-butyl-2,2'-bipyridine) shows a cathodic shift of the phenazine-based reduction process compared to similar molecules, while the first detected reduction wave (-1.34 V vs Fc/Fc(+)) is assigned to the imidazole unit within the molecule. On the basis of the TD-DFT calculations, the strong visible absorption band exhibited by Cl is assigned to a metal-to-ligand charge transfer (MLCT) transition with a concurrent ligand-centered (LC) transition. At room-temperature, Cl features emission (Phi = 0.04) from its lowest excited states with time constants of 1.2 and 18.3 mu s. These lifetimes are assigned to emission processes from the (MLCT)-M-3 and (LC)-L-3 state, respectively. This is the first time that a long-lived dual emission has been observed for a ruthenium(II) complex bearing a directly fused extended pi-system. Furthermore, the emission of C1 is quenched upon water addition. In contrast to related compounds based on a dipyridophenazine ligand, the excited state energy is not shifted, and the lifetime is drastically decreased to 169 ns.