The excited-state dynamics of two mixed-ligand mononuclear ruthenium(II) complexes [(bpy)(2)RuLDQ](4+) (where bpy = 2,2`-bipyridine, L-DQ = 1-[4-(4`-methyl)-2,2 -bipyridyl)]-2-[4-(4`-N,N`-tetramethylene-2 2`-bipyridinium]) and [(bpy)(2)RuL](2+) (where L = 1, 2-bis[4-(4`-methyl)-2,2`-bipyridyl)Jethene), were investigated by femtosecond transient absorption spectroscopy Photoexcitation of the [(bpy)(2)RuLDQ](4+) complex at three separate pump wavelengths leads to a common charge-separated state consisting of Ru3+ and an excited electron delocalized over the extended pi-system centered on the ethenyl moiety of the L-DQ ligand In [(bpy)2RuL]2+, the excited electron is unable to delocalize throughout the pi system and remains on the bipyridyl end of ligand L closest to the ruthenium atom Vibrational cooling in the charge-separated state of [(bPY)(2)RuLDQ](4+) indicates that this state is formed faster than excess energy can be dispersed to the solvent and orders of magnitude more rapidly than in previously studied ruthenium-diquat or ruthenium-viologen dyads with nonconjugated linkers