Metal Sm has been widely used in making Al–Sm magnet alloy materials. Conventional distillation technology to produce Sm has the disadvantages of low productivity, high costs, and pollution generation. The objective of this study was to develop a molten salt electrolyte system to produce Al–Sm alloy directly, with focus on the electrical conductivity and optimal operating conditions to minimize the energy consumption. The continuously varying cell constant(CVCC) technique was used to measure the conductivity for the Na_3 AlF_6–AlF_3–LiF–MgF_2–Al_2O_3–Sm_2O_3 electrolysis medium in the temperature range from 905 to 1055°C. The temperature(t) and the addition of Al_2O_3(W(Al_2O_3)), Sm_2O_3(W(Sm_2O_3)), and a combination of Al_2O_3 and Sm_2O_3 into the basic fluoride system were examined with respect to their effects on the conductivity(κ) and activation energy. The experimental results showed that the molten electrolyte conductivity increases with increasing temperature(t) and decreases with the addition of Al_2O_3 or Sm_2O_3 or both. We concluded that the optimal operation conditions for Al–Sm intermediate alloy production in the Na_3 AlF_6–AlF_3–LiF–MgF_2–Al_2O_3–Sm_2O_3 system are W(Al_2O_3) + W(Sm_2O_3) = 3wt%, W(Al_2O_3):W(Sm_2O_3) = 7:3, and a temperature of 965 to 995°C, which results in satisfactory conductivity, low fluoride evaporation losses, and low energy consumption. Metal Sm has been widely used in making Al-Sm magnet alloy materials. Conventional distillation technology to produce Sm has the disadvantages of low productivity, high costs, and pollution generation. The objective of this study was to develop a molten salt electrolyte system to produce The continuous varying cell constant (CVCC) technique was used to measure the conductivity for the Na_3 AlF_6-AlF_3-LiF-MgF_2-Al_2O_3- Sm_2O_3 electrolysis medium in the temperature range from 905 to 1055 ° C. The temperature (t) and the addition of Al_2O_3 (W (Al_2O_3)), Sm_2O_3 (W (Sm_2O_3)), and a combination of Al_2O_3 and Sm_2O_3 into the basic fluoride system were examined with respect to their effects on the conductivity (κ) and activation energy. The experimental results showed that the molten electrolyte conductivity increases with increasing temperature ( We concluded that the optimal operation conditions for Al-Sm intermediate alloy production in the Na_3 AlF_6-AlF_3-LiF-MgF_2-Al_2O_3-Sm_2O_3 system are W (Al_2O_3) + W (Sm_2O_3) = 3 wt%, W (Al_2O_3): W (Sm_2O_3) = 7: 3, and a temperature of 965 to 995 ° C, which results in satisfactory conductivity, low fluoride evaporation losses, and low energy consumption.