Flower-like ZnO nanostructures, which consisted of sword-like ZnO nanorods, have been prepared by an organic-free hydrothermal process. The XRD pattern indicated that the flower-like ZnO nanostructures were hexagonal. The SAED and HRTEM experiments implied that the sword-like ZnO nanorods were single crystal in nature and preferentially grew up along the  direction. The effects of temperature, pH value and mineralizer on the morphology have been also investigated. It is considered that pH value is the main factor to influence the morphology because of its effect on the initial nuclei and growth environment of ZnO. Finally, the mechanism for organic-free hydrothermal synthesis of the flower-like ZnO nanostructure is discussed.