A series of Ru(II) complexes were synthesized with the deprotonated forms of the ligands 8-hydroxyquinoline (quo−) and 5-NO2-8-hydroxyquinoline (5-NO2-quo−) as analogs to the prototypical complex [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine). Electrochemistry, spectroscopy and density functional theory calculations were utilized to investigate the electronic tuning of the occupied t2g-type orbitals of the metal center with variation in the ligation sphere. The maximum of the lowest energy absorption of complexes containing one, two and three 8-quinolate ligands progressively redshifts from 452 nm in [Ru(bpy)3]2+ to 510 nm in [Ru(bpy)2(quo)]+, 515 nm in [Ru(bpy)(quo)2] and 540 nm in [Ru(quo)3]− in water. This bathochromic shift results from the increase in energy of the occupied t2g-type orbital across the series afforded by coordination of each subsequent quo− ligand to the Ru(II) center. Time-dependent density functional theory calculations along with electrochemical analysis reveals that the lowest energy transition has contributions in the highest occupied molecular orbital from both the quo− ligand and the metal, such that the lowest energy transition is not from an orbital that is purely metal-centered in character as in [Ru(bpy)3]2+.