A simple and highly sensitive extraction-spectrophotometric determination of mercury is described. The ion-associate formed between the HgI(4)(2-) and toluidine blue-O is extracted with dichloromethane at pH 6. The absorption maximum of the extracted species occurs at 593 nm, the molar absorptivity being 1.42 x 10(5) L mol(-1) cm(-1). The calibration curve was linear in the concentration range of 0.1-2.5 mu g mL(-1) of Hg(2+) with a correlation coefficient of 0.9995. The limit of detection (LOD) is 0.021 mu g mL(-1). The relative standard deviation (RSD) at 0.6 and 1.2 mu g mL(-1) of mercury were 2.12 and 3.08 % (n = 8), respectively. The method was applied for measuring the amount of mercury in water samples.