BiVO4/cobalt phthalocyanine (CoPc) hierarchical nanostructures were prepared. The structural and photochemical properties were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), UV-vis diffuse reflectance spectroscopy (DRS) and Brunauer-Emmett-Teller (BET) surface area test. The samples are well-defined hierarchical nanostructures, and their absorption was extended to the near-infrared region. The photocatalytic activities of the BiVO4/CoPc photocatalysts were evaluated by the decomposition of methylene blue (MB) under visible light irradiation and showed excellent visible light photocatalytic performances compared to BiVO4 nanofibers.