Nanoparticles, microsphere, hedgehog sphere-like and flower-like ZnO:Fe photocatalysts were prepared by the hydrothermal method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet/visible absorption spectra (UV-Vis). The results show that the ZnO:Fe photocatalysts with different 3D morphologies are a hexagonal wurtzite structure with space group of p63mc. The pH value of the precursor has a great influence on various morphologies of ZnO:Fe photocatalysts. The flower-like and hedgehog sphere-like ZnO:Fe photocatalysts exhibit the high solar photocatalytic behavior on methylene blue (MB). The ZnO:Fe order of photocatalytic activity is as follows: flower [ hedgehog sphere [ microsphere [ nanoparticle. The flower-like ZnO:Fe is optimal, which exhibits the highest degradation rate of 98% for light time of 5 h.