Molten CaCl2 has been considered as significant electrolyte for novel electrochemical metallurgy processes due to high solubility of oxygen anions. Some novel processes based on molten-salt electrolysis of oxides in molten chlorides have been proposed, typically including FFC process and OS process. An inert anode capable of sustained oxygen evolution is crucial for a green and efficient electrochemical de-oxidation process. Herein we report the results of a promising inert anode candidate, who shows an excellent performance. Several techniques including anodic polarization, cyclic voltammetry, Tafel polarization and electrochemical impedance have been performed to evaluate the anode behavior of the TiO2 center dot RuO2 anode, revealing that the anode is quite stable during anodic polarization and has a more positive corrosion electrode potential. An in situ analysis of anode gases using the mass spectra proved the capability of the sustained evolution of oxygen at the TiO2 center dot RuO2 anode during electrolysis, meaning that this oxides anode could be a potential candidate as inert anode in calcium chloride-calcium oxide melts for green metallurgical processes, as it showed a nearly negligible solubility of ruthenium dioxide when immersed in the melt and a low rate of corrosion even after long time electrolysis. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@ electrochem.org. All rights reserved.