Phosphorus is an essential nutrient for organisms growth and a major cause of eutrophication in water bodies. Thus, it is crucial for both of the removal and recovery of phosphate from wastewater. In this work, the NiCo-layered double oxide (NiCo-LDO) was successfully fabricated on carbon cloth conductive substrate via the in-situ calcination of the NiCo-layered double hydroxide (NiCo-LDH) and served as the electrochemically switched ion exchange (ESIX) film electrode for the removal and recovery of PO₄^3-. The performance of NiCo-LDO for PO₄^3- removal by ESIX and ion exchange (IX) was compared, while the selectivity and stability of NiCo-LDO for PO₄^3- removal were also investigated. The results revealed that, in (10.00±0.05) mg/L PO₄^3- solution, the ion exchange quantity of the NiCo-LDO for PO₄^3- removal by ESIX process was about twice over that by IX. Moreover, compared with Cl ^-, NO₃^-, SO₄^2- and I ^-, the NiCo-LDO exhibited much higher selectivity towards PO₄^3-. In addition, the ion exchange quantity still retained 92% of its initial value after 5 uptake and release cycles. Coupled with XPS analysis, it was found that ESIX process of NiCo-LDO film electrode for PO₄^3- removal and recovery mainly consisted of 3 steps, which were an irreversible “memory effect” structure recovery process, the redox reaction of metal ion in lamellar and the ligand exchange between PO₄^3- and O-H groups.