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The variation in both the discharge characteristic and microstructure during aging for Mg–Zr–O protective films was investigated. In the aging process, the firing voltage and the minimum sustain voltage were reduced by 18 V and 10 V, respectively. Meanwhile, the results of x-ray photoelectron spectroscopy (XPS) measurement revealed that the valence band edge of Mg–Zr–O protective films was slightly shifted to a low binding state and the density of states for valence bands was increased. The electronic structure variation related to the changes in crystal structure had an obvious influence on the improvement of discharge characteristic of Mg–Zr–O films.