A study on the electrosorption of Co2+ and Sr2+ ions onto a porous activated carbon fiber (ACF) was performed to treat radioactive liquid wastes resulting from chemical or electrochemical decontamination and to regenerate the spent carbon electrode. The result of batch electrosorption experiments showed that applied negative potential increased adsorption kinetics and capacity in comparison with open-circuit potential (OCP) adsorption for Co2+ and Sr2+ ions. The adsorbed Co2+ and Sr2+ ions are released from the carbon fiber by applying a positive potential on the electrode, showing the reversibility of the sorption process. The possibility of application of the electrosorption technique to the separation of radionuclides was examined. The result of a selective removal experiments of a single component from a mixed solution showed that perfect separation of Co2+ and Sr2+ ions was possible by the electrosorption process.