The cathodic reduction reaction of Ce(III) ions to metal on an inert Mo electrode in fused 3LiCl–2KCl eutectic at the temperature range 723–823 K by stationary and non-stationary electrochemical methods was investigated. It was found that only one cathode current peak at a potential of –3.19 ± 0.10 V and the corresponding to it one anode current peak at a potential of –3.10 ± 0.08 V vs. the chlorine reference electrode were fixed on voltammograms. Therefore, the recovery process was preceded by the following reaction Ce3+ + 3ē → Ce. Analysis of cyclic voltammograms showed that the cathode potential peak of Ce(III) ions shifts to the negative side with the increasing scan rate. At the same time, the cathode current peak is directly proportional to the square root of the polarization rate at the entire potential range. It was shown that the increasing of scan rate leads to a decrease of the transfer coefficient (α), i.e., an increase of the irreversibility of the cathode process. According to the theory of cyclic voltammetry, the cathode recovery process of cerium ions is irreversible, proceeds in one stage and is controlled by the charge transfer rate. The dependence of the apparent standard potential of the Ce(III)/Ce couple vs. the temperature was determined by the chronopotentiometry method at zero current. The experimental values are described by the following linear equation: E_{{{{{\text{Ce}}\left( {{\text{III}}} \right)} \mathord{\left/ {\vphantom {{{\text{Ce}}\left( {{\text{III}}} \right)} {{\text{Ce}}}}} \right. \kern-\delimiterspace} {{\text{Ce}}}}}}^{{\text{*}}} = - \left( {{\text{3}}{\text{.455}} \pm {\text{0}}{\text{.010}}} \right) + The apparent standard Gibbs energy change, enthalpy, and entropy of the cerium trichloride formation reaction from its elements in the fused 3LiCl–2KCl eutectic and the activity coefficient of CeCl3 were calculated.