The deposition of photocatalytic TiO₂ coatings with plasma spraying is attractive for large-scale applications due to its low cost and simplicity, but it is still a challenge to obtain a TiO₂ coating with high anatase content. The solidification pathway of inflight melted particles was investigated in the present paper, and TiO₂ coatings with enhanced photocatalytic activity were obtained without a significant loss of the microhardness. The coating microstructure, phase composition, and crystallite size were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Photocatalytic performance was evaluated by decomposing an aqueous solution of methylene blue. Results showed that the anatase content in TiO₂ coating was augmented to 19.9% from 4%, and the time constant of the activity was increased to 0.0046 h⁻¹ from 0.0017 h⁻¹.