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Extended X-ray absorption fine structure (EXAFS) investigation of the oxygen-rich titania formed via the thermal treatment of N-doped TiO2 has revealed that the removal of N-dopants is responsible for the creation of defect sites in the titanium environment, thus triggering at high temperatures (500-800 °C) the capture of atmospheric oxygen followed by its diffusion toward the vacant sites and formation of interstitial oxygen species. The effect of the dopants on Ti coordination number and Ti-Oint and Ti-Nint bond distances has been estimated. The photocatalytic p-cresol degradation tests have demonstrated that the interband states formed by the N-dopants contribute to a greater extent to the visible-light activity than the oxygen interstitials do. However, under the UV irradiation the oxygen-rich titania shows higher efficiency in the pollutant degradation, while the N-dopants in N-TiO2 play the role of recombination sites. The presence of the surface nitrogen species in TiO2 is highly beneficial for the application in partial photooxidation reactions, where N-TiO2 demonstrates a superior selectivity of 5-hydroxymethyl furfural (HMF) oxidation to 2,5-furandicarboxaldehyde (FDC). Thus, this work underlines the importance of a rational design of nonmetal doped titania for photocatalytic degradation and partial oxidation applications, and it establishes the role of bulk defects and surface dopants on the TiO2 photooxidation performance.