A new method for Cr(III) speciation in seven kinds of environmental and biological samples by Fe3O2@ZrO2 nanoparticles magnetic solid phase extraction (MSPE) and flame atomic absorption spectrometry (FAAS) has been developed. Fe3O2@ZrO2 nanoparticles were simply prepared by sol-gel method, and the adsorptive behaviors of Cr(III) and Cr(VI) on Fe3O2@ZrO2 nanoparticles were assessed. At pH 8.0-9.0, Fe3O2@ZrO2 nanoparticles were selective towards Cr(III) but hardly Cr(VI). The retained Cr(III) was subsequently eluted with 3.0 mL of 0.5 mol L-1 HNO3 followed by magnetic decantation. Total chromium was determined after reduction of Cr(VI) to Cr(III) by ascorbic acid. Various parameters affecting Fe3O2@ZrO2 nanoparticles MSPE were optimized systematically. Under the optimum conditions, the adsorption capacity of Fe3O2@ZrO2 nanoparticles for Cr(III) is 22.5 mg g(-1) . With an enrichment factor (EF) of 25, detection limit of Cr(III) was 0.69 ng mL(-1), and the proposed method has been successfully applied for Cr(III) speciation in seven kinds of environmental and biological samples with satisfactory results. (C) 2012 Elsevier B. V. All rights reserved.