The salt removal capacity (SRC) of the carbon electrodes in membrane capacitive deionization (MCDI) is limited by the applied potential ( < 1.6 V). Thus, enhancement of the SRC is essential before applying MCDI to seawater desalination. This study aims at developing a novel MCDI system for seawater desalination by applying overpotential (OP) to enhance ion-adsorption capacity and kinetics, and by reversing the polarity (RP) of electrodes to improve ion-desorption kinetics (hereafter named OP-MCDI-RP) for seawater desalination. At 2.4 V, the OPMCDI system with mesoporous carbon demonstrated a SRC value of 64.7 mg g(-1) when desalting 0.5 M NaCl solution, while the OP-CDI system could only remove 8.2 mg g(-1) under identical conditions. Similarly, an OP-MCDI cell using carbon aerogel demonstrated a greater SRC value of 43.4 mg g(-1 )in comparison with 12.5 mg g(-1) achieved in OP-CDI. These results indicate that the OP-MCDI system can directly desalt high salinity water regardless of the electrode material. In contrast to the OP-MCDI system, the OP-MCDI-RP system yields a higher regeneration efficiency by applying a reversed low-voltage. It is shown that, under appropriate operating conditions, the OP-MCDI-RP system reduced the electrical conductivity of a seawater sample of 37 practical salinity units by 99.9%, suggesting that the OP-MCDI-RP system can be employed for seawater desalination. Due to the dramatic increase in energy demand and insufficient long-term stability caused by high potential and high salt concentration, however, the OP-MCDI-RP process should be further investigated for potential practical applications.