One-dimensional 2,9,16,23-tetra-nitrophthalocyanine iron(II) (TNFePc)/TiO 2 nanofiber heterostructures have been successfully obtained by a simple combination of electrospinning technique and solvothermal process. The as-obtained products were characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and IR spectrum. The results revealed that the TNFePc nanosheets were successfully grown on the primary TiO 2 nanofibers. And, the coverage density of the secondary TNFePc nanostructures could be controlled by adjusting the experimental parameters. Photocatalytic tests displayed that the H 2 O 2 assisted TNFePc/TiO 2 nanofiber heterostructures (TNFePc/TiO 2 –H 2 O 2 ) possessed a much higher degradation rate of methyl orange than the pure TiO 2 and TNFePc/TiO 2 nanofiber without H 2 O 2 under visible light. Moreover, the TNFePc/TiO 2 nanofiber heterostructures could be easily recycled without the decrease of the photocatalytic activity due to their one-dimensional nanostructural property of TiO 2 nanofibers.