We investigated a Leidenfrost effect in the growth of ZnO nanostructures on silicon substrates by ultrasonic-assisted spray pyrolysis deposition(SPD). Structural and optical properties of the ZnO nanostructures grown by varying the growth parameters, such as substrate temperature, source concentration, and suction rate of the mist in the chambers, were investigated using field-emission scanning electron microscopy, X-ray diffraction, and photoluminescence spectrum analysis. Structural investigations of the ZnO nanostructures showed abnormal evolution of the morphologies with variation of the substrate temperatures. The shape of the ZnO nanostructures transformed from nanoplate, nanorod, nanopencil, and nanoprism shapes with increasing of the substrate temperature from 250 to 450 °C; these shapes were significantly different from those seen for the conventional growth mechanisms in SPD. The observed growth behavior showed that a Leidenfrost effect dominantly affected the growth mechanism of the ZnO nanostructures.