Hydrogen peroxide (H₂O₂) plays diverse biological roles, and its effects in part depend on its spatiotemporal presence, in both intra- and extracellular contexts. A full understanding of the physiological effects of H₂O₂ in both healthy and disease states is hampered by a lack of tools to controllably produce H₂O₂. Here, we address this issue by showing visible-light-induced production of exogenous H₂O₂ by free-standing, gold-decorated silicon nanowires internalized in human umbilical vein endothelial cells. We further show that the photocatalytic production of H₂O₂ is a general phenomenon of gold–silicon hybrid materials and is enhanced upon annealing.