The new complex [Ru(bpy)(4AP)(4))2(+) (1), where bpy = 2,2'-bipyridine and 4AP = 4-aminopyridine, undergoes selective photodissociation of two 4APs upon light excitation of the metal-ligand-to-ligand charge-transfer (MLLCT) band at 510 nm. The photoproducts of the reaction are mer-[Ru(bpy)(4AP)(3)(H2O)](2+) (2a) and trans(4AP)[Ru(bpy)(4AP)(2)(H2O)(2)](2+) (3a). Photodissociation occurs in two consecutive steps with quantum yields of phi(1) = (6.1 +/- 1.0) x 10(-3) and phi(2) = (1.7 +/- 0.1) x 10(-4), respectively. Complex 1 was characterized by combined spectroscopic and theoretical techniques. EXAFS experiments at the Ru K-edge (22 117 eV) of 1 in an aqueous solution gave a Ru-N distance of 2.09 +/- 0.01 angstrom. Photoproducts were characterized by electronic spectroscopy, 1D and 2D NMR, and mass spectrometry. Singlet and triplet excited states of 1 were studied by density functional theory (DFT) and time-dependent DFT for characterizing the optical properties of the complex. In the singlet state, (MC)-M-1 (metal-centered) dissociative states lie 0.65 eV above the main (MLLCT)-M-1 transition in the visible region of the UV-vis absorption spectrum. In the triplet state, the energy difference between these states is not reduced. However, potential energy curves of singlet and triplet excited states of 1 along the Ru-N(axial 4AP) and Ru-N(equatorial 4AP) stretching coordinates show that the release of the first 4AP may occur from the triplet state by mixing of (MLLCT)-M-3 and (MC)-M-3 dissociative states. This mixing is favored when the Ru-N(equatorial 4AP) bond is elongated, explaining the formation of the photoproduct 2a.