During the molten salt electrolysis of magnesium production, water in the magnesium chloride (MgCl2) feedstock poses significant interference, reducing the current efficiency. Employing rare earth chlorides (RECl3) to assist in dehydrating MgCl2 and producing Mg-RE master alloys emerges as an effective strategy. This study investigated the transformation process in the hydrolysis reaction of low-hydrate MgCl2 within the molten salt, examining the electrochemical activity of its hydrolysis products using Cyclic voltammetry (CV). Additionally, a thermodynamic analysis of the reaction between hydrolyzate MgO and RECl3 was performed at electrolysis temperatures. By integrating CV and Square wave voltammetry (SWV) with X-ray diffraction (XRD) analysis, the study explored the alterations in the electrochemically active components of the molten salt system following the addition of RECl3 to the KCl-NaCl molten salt containing MgO.