Photoinduced hydrophilic behavior of TiO₂ thin film synthesized by atomic layer deposition method on p-Si wafer as well on SiO₂-coated glass has been studied. In contrast to the TiO₂ film on SiO₂-coated glass, the TiO₂ film on the Si wafer initially had a moderate hydrophobicity and became more hydrophobic upon visible light exposure. Such a significant difference was explained by the formation of a type-II TiO₂–Si heterostructure that was confirmed by the alteration of the work function. The role of photoelectrons in the mechanism of light-induced hydrophilic conversion of the TiO₂ surface was elucidated, which reduces to the deactivation of both active surface sites responsible for the superhydrophilic transition and already existing hydrophilic sites. Reversible hydrophilic-to-hydrophobic surface conversion upon switching UV exposure by visible light has been demonstrated for TiO₂/Si coatings. Similar to the tensiometric data, a cyclic change in the work function value was found. The observed cycles in values of water contact angle and work function were gradually ceasing. This phenomenon was associated with the formation of the interfacial SiO_x layer as a result of light-induced passivation of silicon at the TiO₂–Si interface.