A method has been developed for the spectrophotometric determination of selenium(IV) using 4-methyl-o-phenylenediamine (MOPDA) as a chromogenic reagent. In hydrochloric acid media at about pH 2, MOPDA forms a piazselenol complex with selenium(IV), which gives an absorption maximum at 332 nm. After transfer of the formed piazselenol complex into organic phase with n-hexane, the absorbance of the piazselenol complex was measured by a UV-Vis spectrophotometer. The effective parameters of the experimental conditions such as pH, formation time of the complex, amount of MOPDA, ionic strength, volume of sample and effects of diverse ions, were investigated. The detection limit of the proposed method was found to be 0.95 mu g/L Se(IV) (n = 14, 3 sigma). The method was successfully applied to tap water, sea water and wastewater samples from washings of flue gases with satisfactory results.