In this work a photosubstitution strategy is presented that can be used for the isolation of chiral organometallic complexes. A series of five cyclometalated complexes Ru(PhbPY)(N-N)(DMSO-kappa S)](PF6) ([1]PF6-[5]PF6) were synthesized and characterized, where Hphbpy = 6'-phenyl-2,2'-bipyridyl, and N-N = bpy (2,2'-bipyridine), phen (1,10-phenanthroline), dpq (pyrazino[2,3-f][1,10]phenanthroline), dppz (dipyrido[3,2-a:2',3'-c]phenazine, or dppn (benzo[i]dipyrido[3,2-a,2',3'-c]phenazine), respectively. Due to the asymmetry of the cyclometalated phbpy-ligand, the corresponding [Ru(phbpy)(N-N)(DMSO-kappa S)](+) complexes are chiral. The exceptional thermal inertness of the Ru-S bond made chiral resolution of these complexes by thermal ligand exchange impossible. However, photosubstitution by visible light irradiation in acetonitrile was possible for three of the five complexes ([1]PF6-[3]PF6). Further thermal coordination of the chiral sulfoxide (R)-methyl ptolylsulfoxide to the photoproduct [Ru(phbPY)(Phen)(NCMe)]FF6, followed by reverse phase HPLC, led to the separation and characterization of the two diastereoisomers of [Ru(phbpy)(phen)(MeSO(C7H7))]PF6, thus providing a new photochemical approach toward the synthesis of chiral cyclometalated ruthenium(II) complexes. Full photochemical, electrochemical, and frontier orbital characterization of the cyclometalated complexes [1]PF6-[5]PF6 was performed to explain why [4]PF6 and [5]PF6 are photochemically inert while [1]PF6-[3]PF6 perform selective photosubstitution.