By means of Delta-SCF and time-dependent density functional theory (DFT) calculations on [Ru(LL)(3)](2+) (LL = bpy = 2,2'-bipyridyl or bpz = 2,2' -bipyrazyl) complexes, we have found that emission of these two complexes could originate from two metal-to-ligand charge-transfer triplet states ((MLCT)-M-3) that are quasi-degenerate and whose symmetries are D-3 and C-2. These two states are true minima. Calculated absorption and emission energies are in good agreement with experiment; the largest error is 0.14 eV, which is about the expected accuracy of the DFT calculations. For the first time, an optimized geometry for the metal-centered (MC) state is proposed for both of these complexes, and their energies are found to be almost degenerate with their corresponding (MLCT)-M-3 states. These [Ru-II(LL)(eta(1)-LL)(2)](2+) MC states have two vacant coordination sites on the metal, so they may react readily with their environment. If these MC states are able to de-excite by luminescence, the associated transition (ca. 1 eV) is found to be quite different from those of the (MLCT)-M-3 states (ca. 2 eV).