A study of the electrochemical behavior of CeCl3 in LiCl-KCl eutectic was performed in the temperature range 653-973K to ascertain if CeCl3 is a suitable surrogate for UCl3 in the development of nuclear fuel cycle technologies. Reduction of cerium occurs in a single 3-electron step that is quasi-reversible. The diffusion coefficient of Ce(III) was determined by linear sweep voltammetry and chronopotentiometry. The standard potential of Ce(III)/Ce(0) was measured and used to calculate Gibbs free energy and the activity coefficient. The nucleation of cerium on a tungsten substrate was determined to be instantaneous with hemispherical nuclei whose growth is controlled by linear or hemispherical diffusion. The order of magnitude of the exchange current density was determined by the linear polarization method. The electrochemical characteristics of CeCl3 were compared with those of UCl3 in LiCl-KCl to evaluate the potential of cerium as a surrogate for uranium electrorefining development. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3575637] All rights reserved.