AbstractSolvated electrons are highly reductive chemical species whose chemical properties remain largely unknown. Diamond materials are proposed as a promising emitter of solvated electrons and visible light excitation would enable solar‐driven CO₂ or N₂ reductions reactions in aqueous medium. But sub‐bandgap excitation remains challenging. In this work, the role of surface states on diamond materials for charge separation and emission in both gaseous and aqueous environments from deep UV to visible light excitation is elucidated. Four different X‐ray and UV–vis spectroscopy methods are applied to diamond materials with different surface termination, doping and crystallinity. Surface states are found to dominate sub‐bandgap charge transfer. However, the surface charge separation is drastically reduced for boron‐doped diamond due to a very high density of bulk defects. In a gaseous atmosphere, the oxidized diamond surface maintains a negative electron affinity, allowing charge emission, due to remaining hydrogenated and hydroxylated groups. In an aqueous electrolyte, a photocurrent for illumination down to 3.5 eV is observed for boron‐doped nanostructured diamond, independent of the surface termination. This study opens new perspectives on photo‐induced interfacial charge transfer processes from metal‐free semiconductors such as diamonds.