Conventional water treatment techniques typically suffer from severe limitations in selective removal and recovery of heavy metals from dilute solutions. For instance, treatment by pH control, chemical reduction, and chemical oxidation result in precipitation of heavy metals, which are subsequently landfilled. Ion exchange suffers from lack of selectivity in cation removal from multi-component mixtures, while electrochemical reduction has severe limitations in dilute solutions. In order to address the problem of selective heavy metal removal and recovery, development of the Membrane-Electrode (M-E) process was undertaken. The M-E process is a hybrid of electrochemical reduction and ion-exchange technologies and permits selective ion-exchange from dilute aqueous solutions. High cation selectivities in the M-E process is due to controlled rate of ion-exchange. It has been discovered that cation exchange rates can be controlled by application of an electrical potential difference (pd), and that an inverse relationship exists between pd and the rate of ion-exchange. This behavior is termed as the "Reverse-Potential Phenomena". Typically, the rate of ion-exchange in conventional ion-exchange processes is dependent upon the cation concentration in solution, and cation loading on the ion-exchange material; this rate cannot be controlled by external means. Thus far, the M-E process has been effectively demonstrated for selective recovery of Pb2+ and Cu2+ ions from dilute aqueous binary and ternary cation solutions [1,2]. This paper focuses on the effect of Reverse-Potential phenomena on selectivity in the Cu2+/Ni2+ binary solution mixture.