The electrode material with high electrosorption capacity and fast electrosorption rate is highly desired in capacitive deionization (CDI) process. To meet this demand, the nitrogen-doped cluster-like porous carbons (NCPCs) with hierarchical hollow nanoarchitecture were rationally prepared by carbonizing the polydopamine/nano-ZnO composite and employed as CDI electrodes. The resultant NCPCs possess an interconnected hierarchical structure with a hollow cavity, nitrogen-doping property, high specific surface, large pore volume and good wettability. All these merits can ensure a huge accessible electrosorption interface for the very quick diffusion of ions so that achieve an excellent CDI performance. Particularly, the sample carbonized at 900 degrees C (NCPC-900) with the optimal porous structure and chemistry composition exhibits the highest electrosorption capacity of 11.98 mg g(-1) in 100 mg L-1 NaCl solution. Besides, the NCPC-900 electrode shows a good cycle stability over 20 electrosorption-desorption cycles. These results render that the NCPCs have the great potential as the electrode material for high performance CDI desalination.