Contaminated industrial effluents often contain a variety of organic pollutants which are difficult to analyse by standard GC-MS methods since this technique often misses the more polar or non-volatile fraction of these organic compounds. In the present work a method for the characterization of complex mixtures of organic contaminants present in various industrial effluents is proposed. The protocol consists of setting-up a methodology based on solid phase extraction (SPE) using an Automated Sample Preparation with Extraction Columns system (ASPEC XL) and Lichrolut EN sorbent material for preconcentrating 300-500 ml of water volumes spiked with a variety of pollutants : phenolic compounds, benzophenone, isothiocyanate-cyclohexane, ethylbenzoate, 1-methyl-2pyrrolidinone, 2-methylbenzenesulphonamide, benzidines, acridine, 1,1,3,3-tetramethyl-2-thiourea, 2,2-dimethyl-1,3-propanediol, phosphates, phthalates and non-ionic detergents characterized by LC-MS using atmospheric pressure chemical ionization in the positive and negative ion modes. The developed protocol permitted unequivocal identiÐcation of target analytes such as pentachlorophenol, tributyl phosphate, 4-nonylphenol, dibutylphthalate, dimethylphthalate, bis(2-ethylhexyl)phthalate, isothiocyanate-cyclohexane, ethylbenzoate, 2-methylbenzenesulphonamide, tetramethyl-thiourea, 2,2-dimethyl-1,3-propanediol and 1-methyl-2-pyrrolidinone at concentration levels varying from 0.16 to 54.4 lg l-1.