NEU-1, a new lunar soil simulant mined from the Longgang Volcano Group in Jilin Province of China, was electrochemically split into Al-Si alloy and oxygen in molten 52.7wt%NaF-47.3wt%AlF3 at 1233 K using 56wt%Fe-44wt%Ni metallic inert anode. The anode gas was analyzed by gas chromatography, while the cathode product obtained by galvanostatic electrolysis for 8 h was analyzed by means of X-ray diffraction, X-ray fluorescence, scanning electron microscopy and energy dispersive spectrometer. The results showed that the phase compositions of the cathode product are Al and Si, while the metallic mass fraction is 56.70 wt% Al, 40.80 wt% Si, 2.25 wt% Fe, and 0.25 wt% Ti, respectively. Besides, the outlet gas on the anode during electrolysis is pure oxygen according to the analysis of gas chromatography.