Zinc oxide (ZnO) microrod arrays were synthesized on Si substrate by a vapor phase transport (VPT) method in a tube furnace. The obtained ZnO microrods are characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photoluminescence (PL) measurement indicates that the ZnO microrods have a strong ultraviolet (UV) emission centered at ~391 nm and a defect-related emission centered at ~530 nm. After the microrods were coated with graphene oxide (GO), the PL intensity of the hybrid microstructure is quenched compared with that of the bare one at the same excitation condition, and the PL intensity changes with the concentration of the GO. The fluorescence quenching mechanism is also discussed in this work.