Carbon hollow spheres (CHS) have been initially employed as promising electrodes for highly efficient capacitive deionization (CDI). When the initial concentration of NaCl is 25 mg/L and cell voltage of 2.0 V, the electrosorption capacity of CHS is 4.8 mg/g. After five cycles of electrosorption–desorption, there is no decay on electrosorption capacity, implying excellent regeneration performance. Remarkably, the electrosorption behavior of CHS electrode can be simulated by a dynamical CDI model for batch-mode operation and the maximum electrosorption capacity of CHS predicted from Langmuir isotherm is 7.17 mg/g while the corresponding value is only 5.82 mg/g for activated carbon.