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A novel N-doped K3Ti5NbO14@TiO2 (NTNT) core-shell heterojunction photocatalyst was synthesized by firstly mixing titanium isopropoxide and K3Ti5NbO14 nanobelt, and then calcinating at 500 °C in air using urea as the nitrogen source. The samples were analyzed by X-ray diffraction pattern (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-Vis absorption spectroscopy and X-ray photoelectron spectroscopic (XPS) spectra. Anatase TiO2 nanoparticles were closely deposited on the surface of K3Ti5NbO14 nanobelt to form a nanoscale heterojunction structure favorable for the separation of photogenerated charge carriers. Meanwhile, the nitrogen atoms were mainly doped in the crystal lattices of TiO2, resulting in the increased light harvesting ability to visible light region. The photocatalytic performance was evaluated by the degradation of methylene blue (MB) under visible light irradiation. The enhanced photocatalytic activity of NTNT was ascribed to the combined effects of morphology engineering, N doping and the formation of heterojunction. A possible photocatalytic mechanism was proposed based on the experimental results.