Nanometer barium-strontium titanate based coated aluminum oxide (ABST) was prepared by the sol–gel method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectrophotometry (FTIR). Its application in speciation of Cr(III) and Cr(VI) from water were studied. The results showed that the nanometer barium-strontium titanate was immobilized on aluminum oxide firmly, becoming a new adsorbent. Two forms of chromium showed different exchange capacities at different pH values, viz. Cr (III) selectively retained at pH 10–13, whereas Cr (VI) retained at pH 1. Hence complete separation of the two forms of chromium is possible. Retained species were eluted with 5mL of 1 mol•L−1 HCl and 1 mol•L−1 NaOH. The Cr(III) and Cr(VI) concentration was measured by atomic absorption spectroscopy. The adsorbent had a promising prospect in the separation of Cr(III) and Cr(VI) in environment water.