ABSTRACT A novel method based on the aluminothermic reduction of TiO2 in Na3AlF6-AlF3-CaF2 molten salts has been proposed to prepare Al-Ti intermetallic alloys in this research. The Al-Ti intermetallic alloy was obtained by reducing dissolved TiO2 in electrolyte molten salt using liquid Al as a reductant at the stirring rate of 200 r/min for 5 min under 960°C, and it was mainly enriched in the Al matrix which was dispersed in molten salts. The lower alloy layers in the melt pool were characterised by X-ray diffraction (XRD), scanning electron microscopy, energy dispersive spectroscopy (SEM-EDS), and X-ray photoelectron spectroscopy (XPS), taking advantage of the specific gravity difference between the molten salt and the alloy. The TiAl3 was the major intermetallic alloys phase formed between Al and Ti according to XRD results. The Al2O3 by-product in the reduction process of TiO2 was dissolved in electrolyte molten salt.