The electrochemical formation of La–Al alloys in LiF–CaF2 molten salt on a molybdenum electrode at 1123 K was investigated by electrochemical techniques, such as cyclic voltammetry, square-wave voltammetry and open-circuit chronopotentiometry. The formation signals of four types of Al–La intermetallic compounds were observed. The Al–La alloy was obtained through galvanostatic electrolysis at 2.5 A·cm−2 for 3 h. The phase composition and microstructure of the electrolytic products were analysed by X-ray diffraction (XRD) and scanning electron microscopy with energy-dispersive spectroscopy (EDS). XRD results show that the phase compositions of the alloys are Al11La3 and Al, and EDS results reveal 26.7 at% La in the alloy.