X-ray excited optical luminescence (XEOL) using an x-ray nanobeam operating in the hybrid bunch mode provides not only a sufficiently high peak power density but also high-quality temporal domain measurements for studying the luminescence dynamics of photonic materials and devices. We used these features to investigate the peculiar emission behavior of the as-grown and rapid thermal annealing (RTA)-treated a-plane MgZnO epi-films, from which an anomalous emission was observed at ∼325 nm, along with a rapid increase in near-band edge (NBE) emission with increasing x-ray irradiation time. This peculiar emission behavior was also observed in the cathodoluminescence spectra obtained under electron beam excitation. Increases in the NBE emission intensity of the RTA-treated a-plane MgZnO epi-film were observed in terms of both photoluminescence and small anomalous emissions of XEOL. This can be explained by the effective transfer of Mg atoms from interstitial sites to suitable sites as a result of RTA treatment. Based on comparison with an a-plane ZnO epi-film without Mg, we conclude that the anomalous emission peak is caused by Mg-related energy states created by the high-dose x-ray or electron beam irradiation. Furthermore, the rapid increase in NBE emission and the reduction in the long decay lifetime can be attributed to charge transfer from the Mg clusters, which are thus responsible for the anomalous emissions.