To further boost the charge separation and photocatalytic activity of TiO2 under visible light, the anatase–rutile mixed-phase nitrogen-doped (N-doped) TiO2 nanoparticles were successfully synthesized through a facile one-step calcining procedure using TiN as raw materials. The crystal phases, morphologies, chemical compositions, textural structures, and optical properties of as-obtained N-doped TiO2 were characterized by the corresponding analytical techniques. The photocatalytic activities of as-fabricated samples were evaluated by degrading 4-chlorophenol (4-CP) and methylene blue (MB) aqueous solution under visible light irradiation. The results revealed that the ratio of rutile to anatase increased with the improvement of sintering temperature, and the sample prepared at 500 °C had the best photocatalytic activity. This might be because it possessed the most appropriate rutile/anatase proportion as well as the nitrogen doping. The transient photocurrent responses, photoluminescence spectra (PL) measurements, and active species trapping experiments were implemented to disclose the photocatalytic mechanism. This work will provide a further insight into the synthesis of highly efficient N-doped TiO2 photocatalysts for organic contaminant removal.