Recently, we have reported luminescence and excitation spectra of the series [Ru(bpy)(3-x)(bpy-d(8))(x)](2+) (x = 0-3) in [Zn(bpy)(3)](ClO4)(2). Two sets of electronic (3)MLCT origins were observed for the x = 1 and x = 2 systems. Our assignments of these two sets as transitions involving either the bpy-h(8) or the bpy-d(8) ligands have been challenged. We have extended our study of deuteration effects and found clear confirmation of our previous assignments. One set of origins is observed in the series [Ru(bpy-d(x))(3)](2+) (x = 0, 2, 6, 8), and the origins shift gradually to higher energy with increasing deuteration degree. The [Ru(bpy)(bpy-d(8))(2)](2+) complex was further deuterated or protonated to [Ru(bpy-d(2))(bpy-d(8))(2)](2+) and [Ru(bpy)(bpy-d(6))(2)](2+), respectively. Transitions involving the bpy-d(2) and the bpy-d(6) ligand shift to higher and lower energy, respectively, whereas transitions involving the bpy-d(8) or the bpy-h(6) ligand remain at the same energy as in the [Ru(bpy)(bpy d(8))(2)](2+) complex.