Light energy is a driver for many biogeochemical element cycles in aquatic systems. The sunlight-induced photochemical reduction of ferric iron (Fe(iii) photoreduction) to ferrous iron (Fe(ii)) by either direct ligand-to-metal charge transfer or by photochemically produced radicals can be an important source of dissolved Fe in aqueous and sedimentary environments. Reactive oxygen species (ROS) are formed by a variety of light-dependent reactions. Those ROS can oxidize Fe(ii) or reduce Fe(iii), and due to their high reactivity they are key oxidants in aquatic systems where they influence many other biogeochemical cycles. In oxic waters with circumneutral pH, the produced Fe(ii) reaches nanomolar concentrations and serves as a nutrient, whereas in acidic waters, freshwater and marine sediments, which are rich in Fe(ii), the photochemically formed Fe(ii) can reach concentrations of up to 100 micromolar and be used as additional electron donor for acidophilic aerobic, microaerophilic, phototrophic and, if nitrate is present, for nitrate-reducing Fe(ii)-oxidizing bacteria. Therefore, Fe(iii) photoreduction may not only control the primary productivity in the oceans but has a tremendous impact on Fe cycling in the littoral zone of freshwater and marine environments. In this review, we summarize photochemical reactions involving Fe, discuss the role of ROS in Fe cycling, and highlight the importance of photoreductive processes in the environment.