We report an X-ray absorption near edge structure (XANES) study of vanadium (V) and nitrogen (N) dopants in anatase TiO2 thin films deposited by radio-frequency magnetron sputtering. Measurements at the Ti K and V K edges were combined with soft X-ray experiments at the Ti L2,3, O K and N K edges. Full potential ab initio spectral simulations of the V, O and N K-edges were carried out for different possible configurations of substitutional and interstitial dopant-related point defects in the anatase structure. The comparison between experiments and simulations demonstrates that V occupies substitutional cationic sites (replacing Ti) irrespective of the film structure and dopant concentration (up to 4.5 at%). On the other hand, N is found both in substitutional anionic sites (replacing O) and as N2 dimers within TiO2 interstices. The dopants’ local structures are discussed with reference to the enhanced optical …