A novel method for the separation and preconcentration of Cr(III)/Cr(VI) with Lemna minor and determination by slurry atomization electrothermal atomic absorption spectrometry (ETAAS) was developed. A sample solution was added to a polyethylene beaker containing 10 mg of 160 mesh pre-treated Lemna minor, adjusted to pH 1.0, stirred for 8 min for selective absorption of Cr(III) and then centrifuged. The upper layer of solution was transferred into another polyethylene beaker containing 10 mg of 160 mesh pre-treated Lemna minor, adjusted to pH 5.0, stirred for 12 min for adsorption of the residual Cr(VI) and centrifuged. The two residues in two centrifuge tubes were washed twice with water, 2 ml of agar solution added, stirred for 2 min, then two slurries were prepared and used for the determination of Cr(III) and Cr(VI) by ETAAS. Detection limits (3sigma) of 0.01 microg L(-1) for Cr(III) and 0.03 microg L(-1) for Cr(VI) were obtained. The relative standard deviation was 2.8% for Cr(III) and 3.3% for Cr(VI) at the 1 microg L(-1) level. The method was applied to the determination of Cr(III)/Cr(VI) in water samples. The analytical recoveries of Cr(III) and Cr(VI) added to samples were 97-102 and 96-103%, respectively.