Water defluoridation still remains challenge since most of currently applied fluoride adsorbents always have low adsorption capacity with difficulty in regeneration. Herein, NiMn-layered double hydroxide (NiMn-LDH) nanosheets coated conductive multiwalled carbon nanotubes (MWCNTs) were successfully fabricated on the electrode via a unipolar pulse electrodeposition (UPED) method for efficient water defluoridation. It is found that the NiMn-LDH nanosheets with large surface areas can be grafted uniformly on the skeleton of conductive MWCNTs to facilitate the electron transport. Compared to ion exchange (IX) process, faster and more efficient reversible uptake/release of fluoride ions (F-) was realized by modulating the positive and negative charges on the electrical double layer (EDL) of the composite, coupling with ligand exchange at the active sites of NiMn-LDH during the electrochemical redox process. Especially, in a broad pH range (4-10), the electroactive MWCNTs@NiMn-LDH can remove F- effectively. Moreover, the F- adsorption onto MWCNTs@NiMn-LDH followed the pseudo-second-order model, with the maximum F- adsorption quantity of 135.1 mg/g from the Langmuir model. After 5 uptake/release cycles, ion exchange quantity still retained 92.4% of its initial value. Furthermore, the EDL ion transport coupled with ligand exchange mechanism in MWCNTs@NiMn-LDH was verified by XPS analysis. The continuous F- separation runs implied that the flux of F- by MWCNTs@NiMn-LDH was twice over that of by MWCNTs only while the time of the concentration reached even below WHO standard was quarter of that of by MWCNTs only. It is concluded that the MWCNTs@NiMn-LDH is a promising electroactive material for defluoridation, especially combining it in electrochemically switched ion permselective (ESIP) system can realize a continuous F- separation.