A rapid, highly sensitive and selective spectrophotometric method for the determination of traces of selenium(IV) is described. The method is based on oxidation of p-nitroaniline by selenium(IV) followed by coupling reaction with N-(1-naphthalene-1-yl)ethane-1,2-diamine dihydrochloride (NEDA) in neutral medium to give red colored derivative with lambda(max) 515 nm and is stable for more than 10 days at 35 degrees C. Beer's law is obeyed for selenium(IV) in the concentration range of 0.02-3.2 microg ml(-1) at the wavelength of maximum absorption. The optimum reaction conditions and other analytical parameters were investigated to enhance the sensitivity of the present method. The detailed study of various interferences made the method more selective. The proposed method was successfully applied to the analysis of selenium in polluted water, natural water samples, plant material, soil samples, and synthetic mixtures. The results obtained were agreed with the reported methods at the 95% confidence level. The performance of proposed method was evaluated in terms of Student's t-test and Variance ratio f-test which indicates the significance of proposed method over reported method.