In this work, we demonstrate an effective anion capturing in an aqueous medium using a highly porous carbon paper decorated with ZnO nanorods. A sol–gel technique was first employed to form a thin and compact seed layer of ZnO nanoparticles on the dense network of carbon fibers in the carbon paper. Subsequently, ZnO nanorods were successfully grown on the pre-seeded carbon papers using inexpensive chemical bath deposition. The prepared porous electrodes were electrochemically investigated for improved charge storage and stability under long-term operational conditions. The results show effective capacitive deionization with a maximum areal capacitance of 2 mF/cm2, an energy consumption of 50 kJ per mole of chlorine ions, and an excellent long-term stability of the fabricated C-ZnO electrodes. The experimental results are supported by COMSOL simulations. Besides the demonstrated capacitive desalination application, our results can directly be used to realize suitable electrodes for energy storage in supercapacitors. © 2022, The Author(s).