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Fluorinated compounds are effective mineralization agents for the fabrication of plate-like α-Al[sub.2]O[sub.3]. However, in the preparation of plate-like α-Al[sub.2]O[sub.3], it is still an extremely challenging task to reduce the content of fluoride while ensuring a low synthesis temperature. Herein, oxalic acid and NH[sub.4]F are proposed for the first time as additives in the preparation of plate-like α-Al[sub.2]O[sub.3]. The results showed that plate-like α-Al[sub.2]O[sub.3] can be synthesized at a low temperature of 850 °C with the synergistic effect of oxalic acid and 1 wt.% NH[sub.4]F. Additionally, the synergistic effect of oxalic acid and NH[sub.4]F not only can reduce the conversion temperature of α-Al[sub.2]O[sub.3] but also can change the phase transition sequence.