A highly sensitive and selective method has been proposed for direct speciation determination of trace amounts of chromium in water samples using quercetin. The method is based on mixing 5 mL of diluted quercetin solution dissolved in n-amyl alcohol with 5 mL of acidic solution (pH 1) of Cr(VI), which is accomplished with luminescence quenching of the organic phase due to partially oxidation Of quercetin content. Cr(VI) is determined by measuring the diminished content of quercetin with spectrofluorometric method (lambda(ex) = 276 nm, lambda(em)= 331 nm). After oxidation of the Cr(III) content to Cr(VI) and determination of the total chromium as Cr(VI), the Cr(III) is obtained by subtracting. All the variables were studied in order to optimize the reaction conditions. No considerable interference was observed due to the presence of co-existing anions and cations. The calibration graphs were linear in the range 1.0 x 10(-7) to 2.0 x 10(-6) m with the detection limits of 9.1 x 10(-9) M. The R.S.D. obtained for 1.0 x 10(-6) M of Cr(VI) was 17% (n = 7). Validation of the measurements was confirmed using standard reference materials. The method was applied to determine the chromium species in natural water samples. The recoveries obtained for the spiked amount of chromium species were >98%, which denote on satisfactorily application of the method. (C) 2009 Published by Elsevier B.V.