A multicomponent analysis method based on principal component analysis-artificial neural network models (PC-ANN) is proposed for the determination of phenolic compounds. The method relies on the oxidative coupling of phenols (phenol, 2 chlorophenol, 3-chlorophenol and 4chlorophenol) to N.jV-diethyl-p-phenylenediamine in the presence of hex acyanoferrate(l 11). The reaction monitored at analytical wavelength 680 mn of the dye fortned. Phenols can be determined individually over the concentration range 0. 1-7.0 Rg ml-'. Differences in the kinetic behavior of the four species were exploited by using PC-ANN, to resolve mixtures of phenol. After reducing the number of kinetic data using principal component analysis, an artificial neural network consisting of three layers of nodes was trained by applying a back- propagati on learning rule. The optimized ANN allows the simultaneous quantitation of four analytes in mixtures with relative standard errors of prediction in the region of 5% for four species. The results show that PC-ANN is an efficient method for prediction of the four analytes. (c) 2008 Elsevier B.V. All rights reserved.