We use a combined, theoretical and experimental, approach to investigate the spectroscopic properties and electronic structure of three ruthenium polypyridyl complexes, Ru(tpy)22+, Ru(tpy)(bpy)(H2O)2+, and Ru(tpy)(bpy)(Cl)+ (tpy = 2,2′:6′,2′′-terpyridine and bpy = 2,2′-bipyridine) in acetone, dichloromethane, and water. All three complexes display strong absorption bands in the visible region corresponding to a metal-to-ligand-charge-transfer (MLCT) transition, as well as the emission bands arising from the lowest lying 3MLCT state. Ru(tpy)(bpy)(Cl)+ undergoes substitution of the Cl− ligand by H2O in the presence of water. Density functional theory (DFT) calculations demonstrate that the triplet potential energy surfaces of these molecules are complicated, with several metal-centered (3MC) and 3MLCT states very close in energy. Solvent effects are included in the calculations via the polarizable continuum model as well as explicitly, and it is shown that they are critical for proper characterization of the triplet excited states of these complexes.