The increasing amount of heavy metal copper ions (Cu2+) in industrial emissions, poses a serious threat to human health, biological environment, and resource scarcity. Capacitive deionization (CDI) is considered as a green and efficient method for desalination. It is crucial to develop high-performance electrodes for efficient operation of CDI that go beyond conventional carbon and yield considerable environmental benefits. Here, metal organic frameworks (MOFs) derived carbon-loaded cobalt metaphosphate (NC-Co(PO3)2) was prepared by lowtemperature gas-solid phosphating for Cu2+ removal as CDI electrode for the first time. NC-Co(PO3)2 demonstrated superior electrode structure and function due to the synergistic effects of electric double layer coupling PO bonds, the binding tendency of metaphosphate groups with Cu2+, and interfacial redox reactions induced by the labile valence state of cobalt. The optimal electrosorption capacity of NC-Co(PO3)2 was 95.41 mg g-1 at 1 V in 50 mL Cu2+ solution with splendid cyclic regeneration capability. Moreover, NC-Co(PO3)2 exhibited excellent selectivity and outstanding electrosorption performance in the presence of multiple coexisting ions and this CDI system realized the purification of actual copper-containing wastewater. A series of characterizations further revealed the specific mechanism of Cu2+ in adsorption-desorption process. Our finding strongly supported NCCo(PO3)2 electrode can extend the CDI platform's capability for effectively removing and retrieving Cu2+ from wastewater.