An automated micellar electrokinetic capillary chromatographic method has been developed in order to determine xanthines, e.g. caffeine, theobromine and theophylline, and chlorogenic acid in samples of yerba mate (Ilex paraguariensis). The target constituents were detected by photodiode array, and quantified by an external standard method. In addition, each constituent was collected separately and identified by EIMS. The method has been used to analyse 30 samples of mate infusions prepared at 30 and 75°C with milled leaves and stems of 14 commercial brands which had been subjected to different elaboration processes. Suspended powdered material of each infusion was also analysed after three sieving steps. There was a remarkable difference in the relative xanthine composition of the finely suspended material, the amount of which varied according to the yerba mate brand, the elaboration process and the temperature of the infusion. The importance of these results with respect to gastrointestinal disorders which have been observed by habitual consumers of mate are discussed. Copyright © 2002 John Wiley & Sons, Ltd.