ZnO nanorods grown by a hydrothermal technique on zinc substrate display an extrinsic free-to-bound electron-acceptor (eA°) luminescence with the A°level located at ∼130 meV above the valence band. The correlation between A°and the presence of structural defects is investigated by recording cathodoluminescence, transmission electron microscopy, and high-resolution electron microscopy images at the same location of the nanorod. The presence of dislocations and stacking faults observed in the nanorods is directly connected to the spatial variations of the luminescence intensity. Our study indicates that the (eA°) signal is quenched by structural defects.SECTION Nanoparticles and Nanostructures Z inc oxide (ZnO) is a wide band gap semiconductor (E gap = 3.36 eV) that can be used in multiple applications such as sensors, biodetectors, optical, solar, and so on.