The ternary system of molten calcium chloride, potassium chloride and sodium chloride is an important electrolyte in the study of TiO2 electro-deoxidation methods. Therefore, the physicochemical data of the CaCl2-KCl-NaCl ternary system is very useful for optimizing of the electrochemical process. In this paper, the electrical conductivity, molar volume and density of molten CaCl2-KCl-NaCl system were predicted through a new generation geometric model. In order to evaluate the reliability of this method, the conductance of some composition points in the ternary system were also measured by electrochemical impedance spectroscopy (EIS) technique. The results show that the predictions of the model were agreed well with the experiment results. It is expected that this method can be used to solve the shortage of the physicochemical data for multicomponent molten systems. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved.