In the present work, 2,9,1423-tetra-nitrophthalocyanine copper(H) (TNCuPc)/TiO2 hierarchical. nanostructures were successfully fabricated by a simple combination method of electrospinning technique and solvothermal processing. Scanning electron microcopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), UV-vis diffuse reflectance (DR), Fourier transform infrared spectrum (FT-IR), X-ray photoelectron spectroscopy (XPS), and thermal gravimetric and differential thermal analysis (TG-DTA) were used to characterize the as-synthesized TNCuPc/TiO2 hierarchical nanostructures. The results showed that the secondary TNCuPc nanostructures were not only successfully grown on the primary TiO2 nanofibers substrates but also uniformly distributed without aggregation. By adjusting the solvothermal fabrication parameters, the TNCuPc nanowires or nanoflowers were facilely fabricated, and also the loading amounts of TNCuPc could be controlled on the TNCuPc/TiO2 hierarchical nanostructural nanofibers. And, there might exist the interaction between TNCuPc and TiO2. A possible mechanism for the formation of TNCuPc/TiO2 hierarchical nanostructures was suggested. The photocatalytic studies revealed that the TNCuPc/TiO2 hierarchical nanostructures exhibited enhanced photocatalytic efficiency of photodegradation of Rhodamine B (RB) compared With the pure TNCuPc or TiO2 nanofibers under visible-light irradiation.