This paper reports the electrochemical behavior of ThF4 in LiCl-KCl molten salt. It proposes a potentiometric method to determine the complexation constants of thorium (IV) with fluorides. The knowledge of these constants leads to calculate the speciation diagram of Th(IV) species as a function of the concentration of fluoride ions in the salt. These results were extrapolate to give an estimation of the activity coefficient of ThF4 in the molten salt LiF-ThF4 (77.5-22.5 mol%). This salt is retained for the molten salt fast reactor system, currently studied as a Generation IV concept in the domain of nuclear energy. (C) 2014 Elsevier Ltd. All rights reserved.