Electrons in the electron/hole creation event are shown to be the prime catalytic agent in photon‐stimulated oxidation enhancement of silicon. Oxidation enhancement in the 10–50% range occurs at only moderate power density levels of visible wavelength light and increases greatly for photon energies just exceeding the conduction‐band edge between SiO2and Si. ‘‘Hot’’‐electron injection into the SiO2is thought to enhance the oxidation via a process of electron attachment to some of the in‐diffusing O2species, with subsequent dissociation into O and O−species. This injected hot‐electron flux reaction with O2is thought to also occur at a reduced level during standard thermal oxidation.