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This work presents a novel electrochemical study on Al-Li alloys via codeposition of Al and Li on a molybdenum electrode from LiCl-KCl-AlCl3 melts at 663 K.Cyclic voltammograms (CVs) showed that underpotential deposition (UPD) of lithium on predeposited aluminium leads to the formation of Al-Li alloys.It is suggested that the reduction of Al(Ⅲ)is companied by that of Li(Ⅰ) at a more negative potential (-2.40 V) from chronoamperograms.Inductively coupled plasma analysis of the deposits indicated that Al-Li alloys with different lithium contents (60–70 wt.%) were obtained via galvanostatic electrolysis at 663 K.And the aluminium contents of Al-Li alloys could be controlled by AlCl3 concentration and the electrolysis parameters.