Abstract This study was performed to determine the feasibility of electrosorptive removal of copper ions from aqueous solutions using a capacitive deionization process. The electrosorptive potential of copper ions was determined using cyclic voltammetry measurements, and copper electrodeposition could be suppressed at a voltage less than 0.8V. Importantly, the experimental results demonstrated a significant enhancement of electrosorption capability of copper ions using the activated carbon electrodes under electro-assistance, associated with electrical double-layer charging. At 0.8V, the equilibrium electrosorption capacity was enhanced to 24.57mg/g based on the Langmuir model, and the electrosorption constant rate was increased to 0.038min−1 simulated by a first-order kinetics model. Moreover, the activated carbon electrode showed great regeneration performance for the removal of low level copper ions. Additional experiments regarding electrosorption selectivity were performed in the presence of sodium chloride, natural organic matter, or dissolved silica. Copper ions that were preferentially electroadsorbed on the electrode surface can be effectively removed in a competitive environment. Therefore, the electrosorption process using activated carbon electrodes can be recommended to treat copper solutions at low concentrations for wastewater treatment and water purification.