Metastable liquid-liquid immiscibility region in the Al2O3–SiO2 system was calculated by a regular solution model using three sets of liquidus data from the stable phase diagrams reported. These calculations indicated that the immiscibility region was richer in Al2O3 composition than those reported before. A miscibility gap calculated using the liquidus data reported by Klug et al. [F. J. Klug, S. Prochazka, and R. H. Doremus, J. Am. Ceram. Soc. 70, 750 (1987)] (model A) ranged from 2.6 to 71 mol % Al2O3 at around 1000 °C, which was the most compatible result with the idea that metastable pseudotetragonal mullite crystallized at around 1000 °C became Al2O3-rich composition due to the immiscibility phase separation before mullitization among three sets of liquidus data.