In this paper, nanostructure zinc oxide (ZnO) hexagonal rods arrays on ZnO granular films coated substrates were fabricated by a simple chemical solution method. The shapes and structures can be controlled by changing the reactants and experimental conditions. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) equipped with energy dispersive spectrometer (EDS), and fluorescence spectrum were used to characterize the structures and luminescent properties. The best reacting condition has been discussed. Urea was found playing an important role in forming rods. The granular films acting as the seed films were proved.