Activated carbon-nickel (II) oxide (AC-NiO) electrodes were studied as materials for the capacitive deionization (CDI) of aqueous sodium chloride solution. AC-NiO electrodes were fabricated through physical mixing and low-temperature heating of precursor materials. The amount of NiO in the electrodes was varied and its effect on the deionization performance was investigated using a single-pass mode CDI setup. The pure activated carbon electrode showed the highest specific surface area among the electrodes. However, the AC-NiO electrode with approximately 10 and 20% of NiO displayed better deionization performance. The addition of a dielectric material like NiO to the carbon material resulted in the enhancement of the electric field, which eventually led to an improved deionization performance. Among all as-prepared electrodes, the AC-NiO electrode with approximately 10% of NiO gave the highest salt adsorption capacity and charge efficiency, which are equal to 7.46 mg/g and 90.1%, respectively. This finding can be attributed to the optimum enhancement of the physical and chemical characteristics of the electrode brought by the addition of the appropriate amount of NiO.