This Article reports detailed extended X-ray absorption fine structure (EXAFS) analysis of spray pyrolysis synthesized TiO₂ thin films to locate the position of nitrogen in N-doped phase pure (anatase) TiO₂ and evaluate Ti−O bond distances and the coordination number of Ti. The thin films were synthesized at three different substrate temperatures viz. 400, 450, and 500°C leading to concomitant occurrence of varying nitrogen concentration (N/Ti) of 0.282, 0.237, and 0.24, respectively. The coordination number extracted from the EXAFS fitting revealed that films synthesized at 450°C are stoichiometric, whereas those synthesized at 400 and 500°C are substoichiometric. The intensity of near edge peaks in XAS was employed to delineate the contribution from both symmetry of TiO6 polyhedra and particle size. The axial and equatorial Ti−O bond distances, corresponding to the different nitrogen concentrations, extracted from the EXAFS fitting, showed good agreement with those calculated from density functional theory calculations quoted in the literature. An increase in the axial and equatorial bond distances with respect to pristine TiO₂ is observed and is attributed to the dominant effect of nitrogen occupancy in the interstitial position.