Nano-calcium titanate-based coated aluminum oxide (ACCTO) was successfully prepared by the citrate acid sol-gel method and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Its application in speciation of Cr(III) and Cr(VI) from water was studied. The conditions of adsorption and elution were investigated. The results show that nanometer calcium titanate could be immobilized on the aluminum oxide firmly, becoming a composite adsorbent. Two forms of chromium showed different adsorption capability at different pH values, Cr (III) selectively retained at pH 8-14, whereas Cr (VI) retained at pH≤2. So separation of the Cr(III) and Cr(VI) is possible. Retained species were eluted with 5mL of 1 mol•L-1 HCl and NaOH. The Cr(III) and Cr(VI) concentration was measured by atomic absorption spectroscopy. The adsorption agent has a promising prospect in removal or enriching and separation of Cr(III) and Cr(VI) in water.