Fluorinated compounds are effective mineralization agents for the fabrication of plate-like α-Al2O3. However, in the preparation of plate-like α-Al2O3, it is still an extremely challenging task to reduce the content of fluoride while ensuring a low synthesis temperature. Herein, oxalic acid and NH4F are proposed for the first time as additives in the preparation of plate-like α-Al2O3. The results showed that plate-like α-Al2O3can be synthesized at a low temperature of 850 °C with the synergistic effect of oxalic acid and 1 wt.% NH4F. Additionally, the synergistic effect of oxalic acid and NH4F not only can reduce the conversion temperature of α-Al2O3but also can change the phase transition sequence.