ZnO nanostructures with different morphology have been successfully fabricated by a simple relative low temperature approach at 90 °C for 5 h without surfactant assistance. These structures can be easily tailed using varied concentrations of sodium hydroxide (NaOH) and different amounts of the hydrazine hydrate (N2H4·H2O). X-ray diffraction (XRD) result proves the formation of ZnO with wurtzite structure. Microstructure as revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicates that the rod-like and chrysanthemum-like ZnO nanostructures contain many radial nanorods, which grow along the  direction. Furthermore, the as-prepared ZnO nanomaterials exhibit high activity on the photo-catalytic degradation of typical persistent organic pollutants (POPs), indicating that they are promising as semiconductor photo-catalysts.