Glutathione-capped metal nanoclusters (Au-x-GSH NCs) which exhibit molecular-like properties are employed as a photosensitizer for hydrogen generation in a photoelectrochemical cell (PEC) and a photocatalytic slurry reactor. The reversible reduction (E-0 = -0.63 V vs RHE) and oxidation (E-0 = 0.97 and 1.51 V vs RHE) potentials of these metal nanoclusters make them suitable for driving the water-splitting reaction. When a mesoscopic TiO2 film sensitized by Au-x-GSH NCs is used as the photoanode with a Pt counter electrode in aqueous buffer solution (pH = 7), we observe significant photocurrent activity under visible light (400-500 nm) excitation. Additionally, sensitizing Pt/TiO2 nanoparticles with Au-x-GSH NCs in an aqueous slurry system and irradiating with visible light produce H-2 at a rate of 0.3 mmol of hydrogen/h/g of Au-x-GSH NCs. The rate of H-2 evolution is significantly enhanced (similar to 5 times) when a sacrificial donor, such as EDTA, is introduced into the system. Using metal nanoclusters as a photosensitizer for hydrogen generation lays the foundation for the future exploration of other metal nanoclusters with well-controlled numbers of metal atoms and capping ligands.