A novel electrochemical recovery method of Co, Cu, Mn and Ni from a reactor based on two immiscible molten phases, to enable selective metal plating, sufficient feedstock dissolution and protection from re-oxidation, was designed and characterized through voltammetry and chronoamperometry. The immiscible phases in the electrolytic cell were NaCl and Na2O-2B(2)O(3) at 1173 K, and the metal feedstock to be recovered was either metal chlorides or metal oxides of Co, Cu, Mn and Ni. Metals could be successfully recovered as plated metal deposits and the formal redox reaction potentials were reported. Metals thermodynamic behavior differences between the cells were analyzed. Analysis of the metal deposits showed that the recovered metals were of high purity (similar to 99%). This offers an alternative method to recycle valuable metals present in the growing e-waste stream. (C) 2016 The Electrochemical Society. All rights reserved.