Zinc oxide (ZnO) microstructures including the ZnO nanorods (R-ZnO), ZnO nanopillars (C-ZnO), and multistage microspheres composed of ZnO nanosheets (M-ZnO) have been synthesized using a two-step hydrothermal approach by adjusting the concentrations of the growth solution. Scanning Electron Microscopy (SEM) was employed to observe the surface morphology of the fabricated samples. X-ray diffraction (XRD) was utilized for the structure characterization, which the results reveal a hexagonal wurtzite ZnO structure in all three samples with different microstructures. X-ray Photoelectron Spectroscopy (XPS) was used to investigate their defects, indicating that the oxygen vacancy ratios were 34.3 %, 21.8 %, and 51.5 % respectively for R-ZnO, C-ZnO, and M-ZnO. The band gaps of R-ZnO, C-ZnO, and M-ZnO, determined through Ultraviolet-Visible Absorption Spectroscopy (UV-Vis), were found to be 3.35 eV, 3.6 eV, and 3.19 eV, respectively. Finally, the photocatalytic performances of the prepared ZnO samples were investigated under simulated sunlight irradiation by observing the degradation of methyl orange, which the M-ZnO samples obtained a superior photocatalytic efficiency of 79 %.