A combined method involving electrochemical oxidation of iodide to iodate at a platinum electrode followed by extraction in CCl4 of ionic associates of iodine-iodide complexes with brilliant green, formed in excess of iodide, was developed for the spectrophotometric quantification of iodide. The slope of the calibration curve yields a molar extinction coefficient of ɛ = 3·105 L mol−1cm−1. This method can be used for the quantification of iodide in the concentration range of 3·10−7 − 3·10−6 mol L−1 with a detection limit of 5·10−8 mol L−1. The interfering effect of other ions on the determination of the iodide concentration was also investigated. The method was successfully applied for the determination of iodide in real samples of NaCl and spring water. Relative standard deviation is 1–2%.