Flower-like ZnO microstructures were successfully synthesized via a facile hydrothermal route without using any surfactants. The morphology of these microstructures can be easily controlled by adjusting the pH of the reaction solution. The possible growth mechanism of ZnO hierarchical microstructures was proposed based on the X-ray powder diffraction (XRD) and scanning electron microscope (SEM) results. The photocatalytic activity studies of ZnO nanocrystals demonstrated their excellent photocatalytic performance in degrading aqueous methylene blue (MB) under UV-A light irradiation. This higher photocatalytic activity of the ZnO nanoplates was mainly attributed to the exposed facets with the higher surface energy.