In this study, the electrosorption selectivity of porous activated carbon (AC) and nickel hexacyanoferrate (NiHCF), which represent two working mechanisms of capacitive electrosorption and redox intercalation, was investigated to separate cations in capacitive deionization (CDI). The cyclic voltammetry diagrams of AC showed the rectangular shape of double-layer charging, while that of NiHCF showed separated peaks associated with redox reactions. The specific capacitance of NiHCF was 143.6 F/g in 1 M NaCl, which was almost two times higher than that of AC. Cation selectivity experiments were conducted in single-pass CDI for a multi-cation solution. The electrosorption preference of the AC cathode was determined by a counterbalance between the ionic charge and hydrated size, reflecting the selectivity coefficient of different cations over Na+ in the range of 0.86–2.63. For the NiHCF cathode, the cation …