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The effects of electron beam irradiation on the luminescence of ZnO single crystals were investigated by cathodoluminescence. We have found that the evolution of the intensity during the e-beam irradiation depends on the surface polarity. For O-face, the ultraviolet (UV) emission decreases exponentially and approaches an asymptotic value. For Zn-face, it first increases and then decreases. The decrease components are similar in both faces. If we halt the e-beam irradiation, the UV intensity recovers partially. These results suggest that the decrease in the UV evolution is related to metastable bulk defect reactions at the subsurface region while the increase is related to surface reaction such as electron-stimulated desorption.