Cyclic voltammetry (CV) and chronoamperometry (CA) were employed to develop a real-time monitoring system for the pyrochemical process. These electrochemical techniques showed a good linearity of the current and the passed charges with the concentration of a solute even up to 9wt.% in a LiCl–KCl melt, showing the potential for real application. To apply CA to the pyrochemical process, where the concentration of actinides and/or lanthanides is largely variable, the repeating chronoamperometry was designed and successfully tested at a wide range of Nd 3+ ion concentration of up to 9wt.%.