In this study, nickel–aluminium complex hydroxides at different molar ratios (nickel–aluminium = 1 : 2, 1 : 1, 2 : 1, 3 : 1, and 4 : 1, referred to as NA12, NA11, NA21, NA31, and NA41) were prepared, and their adsorption capability for chromium(VI) ion was investigated. Firstly, physicochemical characteristics (SEM images, X-ray diffraction (XRD) patterns, specific surface area, amount of hydroxyl groups, and surface pH) of nickel–aluminum complex hydroxide were evaluated. The amount of chromium(VI) ion adsorbed onto NA11 (15.3 mg/g) was greater than that adsorbed onto the other adsorbents. This research elucidated that the amount of chromium(VI) ion adsorbed using nickel–aluminium complex hydroxide was related to the adsorbent surface properties ( r = 0.818–0.875). Subsequently, the adsorbent (NA11) surface before and after adsorption of chromium(VI) ion was evaluated, and chromium energy (577 and 586 eV) detected after adsorption onto the NA11 surface. These results revealed that the NA11 surface properties were very important for the removal of chromium(VI) ion from aqueous solution. In addition, the effects of pH, contact time, and temperature on the adsorption of chromium(VI) ion were evaluated. We confirmed a high recovery percentage of chromium(VI) ion when using sodium hydroxide solution at 10–1000 mmol/L (approximately greater than 80%) in this experimental condition. Thus, NA11 is a promising adsorbent for the removal of chromium(VI) ion from aqueous solution.