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A novel magnesium (Mg) production process utilizing an electrolytic method was investigated for the direct reduction of magnesium oxide (MgO). Electrolysis of MgO was carried out with an applied voltage of 3.0 V using a copper (Cu), silver (Ag), or tin (Sn) cathode and carbon (C) or platinum (Pt) anode in magnesium fluoride (MgF2)−calcium fluoride (CaF2)−sodium fluoride (NaF) at 1273 K or MgF2− lithium fluoride (LiF) at 1083−1093 K. After the electrolysis of MgO in MgF2−CaF2−NaF molten salt, Mg alloys such as Mg2Cu, Cu2Mg, or Mg2Sn phases were produced with current efficiencies of 75.8−85.6% when the concentration of Mg in Mg alloys was 9.1−14.6 mass%. In addition, when the electrolysis of MgO was conducted in MgF2–LiF molten salt, Mg alloys such as Mg2Cu or AgMg phase were produced with current efficiencies of 76.2−81.7% when the concentration of Mg in the Mg alloys was 12.5−13.2 mass%. In addition, to produce high-purity Mg metal from Mg alloys, vacuum distillation was conducted. When vacuum distillation was conducted at 1100−1400 K for a duration of 5 h, the concentration of Mg in the Mg alloys feed decreased from 30.2−34.1 mass% to 0.64−1.75 mass%, and Mg metal with a purity of 99.998−99.999% was obtained under certain conditions. Therefore, the molten salt electrolysis using liquid metal cathode (MSE-LMC) process developed here is feasible for the direct reduction of MgO using an effective and environmentally sound method.