Hierarchically porous carbon-coated zirconium oxide nanocubes (HCZ) derived from metal-organic framework (Zr-UiO-66) have been developed as electrode for hybrid capacitive deionization. The obtained HCZ exhibits a hierarchically porous structure and provides excellent electrical connectivity between metal oxides and carbon nanostructures. An asymmetric capacitive deionization made with HCZ//activated carbon shows a remarkable salt adsorption capacity of 55.17 mg g
1 in 250 mg L
1 aqueous sodium chloride solution at 1.4 V. The present method paves a way for the preparation of other hollow C@metal oxide nanostructures for applications in water environment treatment.