Materials that can selectively store Na and Cl ions in the bulk of their structures and release these ions with good cycle stability can enable the construction of a high capacity, rechargeable desalination cell for use in seawater desalination. In this study, the ability of a nanocrystalline Bi foam electrode to serve as an efficient and high capacity Cl-storage electrode using its conversion to BiOCl was investigated. When Bi as a Cl-storage electrode was coupled with NaTi2(PO4)(3) as a Na-storage electrode, a new type of rechargeable desalination cell, which is charged during desalination and discharged during salination, was constructed. The resulting Bi-NaTi2(PO4)(3) cell was tested under various salination and desalination conditions to investigate advantages and potential limitations of using Bi as a Cl-storage electrode. Slow Cl- release kinetics of BiOCl in neutral conditions and an imbalance in Cl and Na storage (i.e., Cl storage requires three electrons/Cl, while Na storage requires one electron/Na) were identified as possible drawbacks, but strategies to address these issues were developed. On the basis of these investigations, optimum desalination and salination conditions were identified where the Bi/NaTi2(PO4)(3) cell achieved a desalination/salination cycle at +/-1 mA cm(-2) with a net potential input of only 0.20 V. The kinetics of Cl- release from BiOCl was significantly improved by the use of an acidic solution, and therefore, a divided cell was used for the salination process. We believe that with further optimizations the Bi/BiOCl electrode will enable efficient and practical desalination applications.