In this paper a comparative study on the microstructure and photocatalytic performances of titanium dioxide coatings elaborated by various thermal spraying methods (plasma spraying in atmospheric conditions, suspension plasma spraying and high-velocity oxy-fuel spraying) was proposed. Agglomerated spray-dried anatase TiO2 powder was used as feedstock material for spraying. Morphology and microstructural characteristics of the coatings were mainly studied by scanning electron microscopy and X-ray diffraction. The photocatalytic behavior of the TiO2-based surfaces was evaluated from the conversion rate of gaseous nitrogen oxides (NOx). It was found that the crystalline structure strongly depended on the technique of thermal spraying deposition. Moreover, a high amount of anatase was suitable for the photocatalytic degradation of the pollutants. Suspension plasma spraying permitted to retain the original anatase phase and to obtain very reactive TiO2 surfaces for the nitrogen oxides removal.