Mullite nanowhiskers with Al-rich structure were prepared by molten salt synthesis at 1000°C for 3 h in air using silica, amorphous silica, and ultrafine silica as the silica sources. The phase and morphology of the synthesized products were investigated by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, and transmission electron microscopy. A thermogravimetric and differential thermal analysis was carried out to determine the reaction mechanism. The results reveal that the silica sources play an important role in determining the morphology of the obtained mullite nanowhiskers. Clusters and disordered arrangements are obtained using common silica and amorphous silica, respectively, whereas the use of ultrafine silica leads to highly ordered mullite nanowhiskers that are 80-120 nm in diameter and 20-30 μm in length. Considering the growth mechanisms, mullite nanowhiskers in the forms of clusters and highly ordered arrangements can be attributed to heterogeneous nucleation, whereas disordered mullite nanowhiskers are obtained by homogenous nucleation. Mullite nanowhiskers with Al-rich structure were prepared by molten salt synthesis at 1000 ° C for 3 h in air using silica, amorphous silica, and ultrafine silica as the silica sources. The phase and morphology of the synthesized products were investigated by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, and transmission electron microscopy. A thermogravimetric and differential thermal analysis was carried out to determine the reaction mechanism. The results reveal that the silica sources play an important role in determining the morphology of the obtained mullite nanowhiskers . Clusters and disordered arrangements are obtained using common silica and amorphous silica, respectively, whereas the use of ultrafine silica leads to highly ordered mullite nanowhiskers that are 80-120 nm in diameter and 20-30 μm in length. Considering the growth mechanisms, mullite nanowhiskers in the forms of clusters of highly ordered arrangements can be attributed to hete rogeneous nucleation, whereas disordered mullite nanowhiskers are obtained by homogenous nucleation.