Iron(III) Phthalocyanine/BiPO4 (FePc/BiPO4) heterostructures were successfully synthesized by electrospinning combined solvothermal routes. The prepared samples were characterized by scanning electron microscopy, X-ray diffraction, UV-Vis diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, photoluminescence spectroscopy, and electrochemical measurement. The samples are well-defined hierarchical nanostructures, and its absorption was extended to the near-infrared region. The photocatalytic activities of the FePc/BiPO4 photocatalysts were evaluated by the decomposition of methylene blue under visible light irradiation (lambda >= 400 nm). The FePc/BiPO4 heterostructures showed excellent visible light photocatalytic performances. The electrochemical measurement was also performed and the effect of the hierarchical nanostructures on the photocatalytic activities was also discussed.