Here, cobalt sulfide derived from metal organic frameworks (S-Co/MOF) was synthesized and applied in capacitive deionization (CDI) for the selective removal of Cu2+. A series of characterizations confirmed the successful preparation of S-Co/MOF. Under an applied voltage of 1 V and an initial concentration of 25 mg L- 1, the electro-sorption capacity of the S-Co/MOF electrode can reach 57.39 mg g- 1, which is much higher than that of the Co/MOF electrode. Moreover, the S-Co/MOF electrode exhibits excellent cycling stability under continuous operations. The S-Co/MOF shows effective selectivity for Cu2+ when removing copper-plating wastewater with coexisting ions such as Pb2+, Mn2+, Zn2+, and Cd2+. Density functional theory calculations also confirm that the Co/MOF with high binding energy is beneficial to the electro-sorption process. Consequently, the CDI with the S-Co/MOF electrode provides an effective method for the selective removal of copper-plating wastewater, paving the way for innovative electrochemical systems in water treatment applications.