AbstractN‐Doped TiO2 coatings (N‐TiO2) were synthesized and characterized. The effect of the doping process on the physical‐chemical properties and photocatalytic efficiency of Methylene Blue (MB) under visible light irradiation were studied. The bare TiO2 showed only anatase crystalline structure. Furthermore, after the doping process, a slight transition from anatase to rutile was verified. The HRXPS confirmed that the doping process was effective. The N2 sorption using the BET assay showed a slight increase in surface area after the doping process. MB adsorption kinetic showed also a slight increase for doped TiO2 films, showing as best fitting the Langmuir model. Furthermore, a modification on the electronic structure was observed, showed by the modification of the optical absorption profile in the doped material. The results showed that the MB adsorption on N‐TiO2 thin films was endothermic (▵H=11 kJ mol−1) and a spontaneous process (▵G=−6.45 kJ mol−1). We performed DFT calculations to three simulated doped‐structures. The Gap value, the global reactivity indexes and, the Fukui function isosurfaces are presented. Finally, the scavenger tests suggested that and OH⋅ could be the main ROS driving the photocatalytic process.