In this study, uniformly distributed leaf-like ZnO nanostructure on glass substrates had been prepared by a simple two-step method. The structural properties were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activity of the leaf-like ZnO nanostructure had been investigated through the degradation of Rhodamine B under UV illumination and using a ZnO thin film and ZnO nanorods as the references. The results show that the photocatalytic activity of leaf-like ZnO nanostructure is higher than that of the ZnO thin film or ZnO nanorods. This is mainly because the leaf-like ZnO nanostructure has a larger surface area than ZnO thin films or ZnO nanorods. What is more, the leaf-like ZnO nanostructure is very firm on the substrate and its photocatalytic activity can be recycled and is stable.