Recent studies have unraveled the potential of octahedral molybdenum cluster complexes (Mo-6) as relevant red phosphors and photosensitizers of singlet oxygen, O-2((1)Delta(g)), for photobiological applications. However, these complexes tend to hydrolyze in an aqueous environment, which deteriorates their properties and limits their applications. To address this issue, we show that phenylphosphinates are extraordinary apical ligands for the construction of Mo-6 complexes. These new complexes display unmatched lumines-cence quantum yields and singlet oxygen production in aqueous solutions. More importantly, the complex with diphenylphos-phinate ligands is the only stable complex of these types in aqueous media. These complexes internalize in lysosomes of HeLa cells, have no dark toxicity, and yet are phototoxic in the submicromolar concentration range. The superior hydrolytic stability of the diphenylphosphinate complex allows for conservation of its photophysical properties and biological activity over a long period, making it a promising compound for photobiological applications.