Biomass-derived porous carbon materials have a good application prospect in electrosorption because of their low cost, abundant natural resources, and excellent performance. In this work, three-dimensional interconnected structure porous carbon (CPC) was successfully synthesized from waste biomass chestnut shells by carbonization and chemical activation processes. The unique structure of CPC could offer superior double-layer capacitance and excellent conductivity. The as-obtained CPC was applied as an electrosorption electrode. In the deionization experiments, the removal efficiency of the CPC electrode in a 30 mg L-1 chromium(VI) aqueous solution at 1.0 V was 90.5%. The electrosorption follows pseudo-second-order kinetics. The CPC electrode also presented good regeneration performance in the regeneration test. These results demonstrate that the as-prepared carbonaceous material is an ideal material for capacitive deionization electrodes.