Enhancing the capacitive deionization performance requires the inner structure expansion of porous activated carbon to facilitate the charge storage and electrolyte penetration. This work aimed to modify the porosity of coconut-shell activated carbon (AC) through CO2 activation at high temperature. The electrochemical performance of CO2- activated AC electrodes was evaluated by cyclic voltammetry, charge/discharge test and electrochemical impedance spectroscopy, which exhibited that AC-800 had the superior performance with the highest capacitance of 112 F/g at the rate of 0.1 A/g and could operate for up to 4000 cycles. Furthermore, in the capacitive deionization, AC-800 showed salt removal of 9.15 mg/g with a high absorption rate of 2.8 mg/g min and Ni(II) removal of 5.32 mg/g with a rate close to 1 mg/g.min. The results promote the potential application of CO2- activated AC for desalination as well as Ni-removal through capacitance deionization (CDI) technology.