Complete desorption of contaminants from electrode materials is required for the efficient utilization and long service life of capacitive deionization (CDI) but remains a major challenge. The electrodesorption capacity of CDI in the conventional electrode configuration is limited by the narrow electrochemical stability window of water, which lowers the operating potential to approximately 1.2 V. Here, we report a graphite anode–titanium cathode electrode configuration that extends the cathode potential to −1.7 V and provides an excellent (100%) electrodesorption performance, which is maintained after five cycles. The improvement of the cathode potential depends on the redox property of the electrode. The stronger the oxidizability of the anode and reducibility of the cathode, the wider the cathode potential. The complete desorption potential of SO₄²⁻ predicted by theoretical electrochemistry was the foundation for optimizing the electrode configuration. The desorption efficiency of Cl⁻ depended on the ionic strength and was negligibly affected by circulating velocities above 112 mL min⁻¹. This work can direct the design optimizations of CDI devices, especially for reactors undergoing chemisorption during the electrosorption process.