This work concerns directly the extraction of gadolinium from Gd 2O3by co-reduction with Al3+in theLiCl-KCl-AlCl3molten salts on the molybdenum and aluminum electrode, respectively, at temperatureof 773 K. Gibbs energy calculation shows that AlCl3 can favorably chloridize Gd2O3and release Gd3+ions. The electrochemical behaviors of Al3+, Gd3+ and the mechanisms of alloy formation were investi-gated by conducting a series of electrochemical techniques. Four typical signals were observed in cyclicvoltammetry, square wave voltammetry and chronopote...