The optical and electrical properties of ZnO related on the type and the concentration of defects in ZnO crystal. Ion implantation and annealing can change the type and the concentration of defects in ZnO. To understand the variation of defects in ZnO during ion implantation and after different temperature annealing, in situ luminescence measurements of ZnO crystal samples were carried out by ion beam induced luminescence (IBIL) during ion implantation of 2 MeV H⁺ and then after annealing at 473 K and 800 K in vacuum on the GIC4117 tandem accelerator in Beijing Normal University. IBIL spectra of ZnO showtwo emission peaks: UV emission, which is called near band emission (NBE), and visible emission, which is called deep band emission (DBE).The high-intensity of DBE and weak NBE of IBIL spectra of ZnOmay be due to the NBE is intrinsic to ZnO samples and therefore is just visibly observed from samples that are virtually defect-free. With the ion implantation, the destruction of the crystal structure and the arising of a mass of defects, inducing the weak intensity NBE and intense DBE.In addition, the overall IBIL spectra of ZnOreveal decrease intensity with the ion fluence,which indicates that the concentration of luminescence centersdecreases duringion implantation.With the H⁺ fluence, the concentration of the point defects increases. The point defects migrate and subsequently agglomerate into larger defect clusters. These defect clusters serve as traps for catching electrons and holes, which result in the quenching of luminescence centres. Annealing can help todecompose the defect clusters and repair the defects of crystal. However, amounts of defects and clusters still remain in the irradiated sample annealed at 473 K in vacuum, which acted as nonradiative center and suppress the luminescence induced weak intensity of IBIL. Annealing the sample at 800 K in vacuum may facilitate the decomposition of defect clusters during ion irradiation to point defects and the point defect return to the lattice position that can reduce the nonequilibrium defects inside the crystal and improve the crystallinity of the crystal, which increase the intensity of its IBIL.