Capacitive deionization has been developed as a promising desalination alternative for removing ions from aqueous solutions. In this study, the evaluation of capacitive performance was carried out by galvanostatic charge/discharge and cyclic voltammetry experiments. The good capacitive and electrosorption behaviors suggest carbon aerogel not only treated as an electrical double layer capacitor, but also as a potential electrode in capacitive deionization processes. Also, the capacitive deionization characteristics indicate that electrosorption/regeneration can be controlled by polarization and depolarization of each electrode. It implies that sodium and chloride ions are electrostatically held to form electrical double layer on the surface of charged electrodes. The electrosorption performance at different applied voltages and solution concentrations was investigated. It is found that the removal of sodium chloride increases with increasing applied voltage and solution concentration, resulting from stronger electrostatic interactions, higher concentration gradient, and less double layer overlapping effect. Based on Langmuir isotherm, the equilibrium electrosorption capacity at 1.2 V is determined as 270.59 μmol/g. Under this condition, due to the presence of micropores associated with the double layer overlapping, the effective surface area for electrosorption of ions at 1.2 V is estimated in the range of 12.18–14.25 % of the Brunauer–Emmett–Teller surface area. The results provide a fundamental understanding of electrosorption of ions and help promoting capacitive deionization technology for water purification and desalination.