Most TiO₂ photocatalytic reactions for environmental cleanup are the hole-driven oxidation of organics coupled with the dioxygen reduction. Therefore, dioxygen is an essential reagent of TiO₂ photocatalysis and the overall photocatalysis does not proceed in the anoxic condition. Here we demonstrate that the anoxic photocatalytic reactions can be enabled by using a modified TiO₂ with simultaneous surface fluorination and platinization (F-TiO₂/Pt). This anoxic degradation in F-TiO₂/Pt can be related to the substrate-surface interaction and the charge transfer/recombination characteristics that should depend on the surface property of TiO₂. On F-TiO₂/Pt, Pt deposits can serve as a temporary electron reservoir whereas the surface adsorption of organic compounds is hindered by the surface fluorination. Under this condition, while the substrate is oxidized by the mobile OH radical off the surface, the electrons remain trapped in the Pt phase. With this scenario, the overall photocatalytic conversion taking place on F-TiO₂/Pt can be highly enhanced even in the absence of O₂ that serves as a dominant electron acceptor in most photocatalytic reactions.