The main objective of this work is to see the feasibility of using an electrochemical ion-exchange process in line with decontamination for removal of radioactive metal ions from simulated decontaminated solution/metal ion–loaded cation-exchange resin. This could extend the service period of resin, and the volume of radioactive resin (organic) waste generation could be minimized. Simulated decontamination solutions/spent resins were used in the middle section of a three-compartment cell separated by cation-permeable Nafion membranes. Metal ions from this central compartment permeated through the membrane and got deposited on the cathode by application of potential. Process parameters like applied voltage, interelectrode distance, pH, decontamination formulations, and type of membrane were optimized for efficient transport of metal ions. The resin life was observed to be extended by 5 h by an electrochemical regeneration process with Nafion membrane N115. The transport process, as monitored by the change in metal ion concentration in the cathodic compartment, was observed to pass through a maximum. Maximum metal ion removal was observed with formic acid/formate formulation indicating that the presence of acidity in the anodic compartment has a synergistic effect on the transport process. The cathodic compartment deposit was characterized by X-ray diffraction, laser Raman spectroscopy, scanning electron microscopy, and energy dispersive X-ray analysis.