The selective transport for Li-Na and Li-K systems through cation exchange membranes under an electric field was measured as a function of voltage, feed concentration, and the number of membranes used in the chamber. The transfer rate of metal ions and permeation selectivity were evaluated by conducting experiments both in a single and multistage continuous one-pass flow mode of operation. The results are analyzed on the basis of the concentration of alkali metal ions from the feed and recovery side overflows. A comparison of the results obtained from both the single stage and multistage experiments showed that higher selectivity was obtained for the Li-K system compared to the Li-Na system. For the multistage operation, the permeation and selectivity of Li+ and K+ through five and 11 membranes were examined. A high separation factor was obtained when 11 membranes were used. The efficiency of the recovery of metal ions using membranes may be expressed by the calculation of the separation factor and the metal ion concentration obtained from the recovery solution and further enhanced by increasing the number of membranes used.