Abstract The applicability of distillation to concentrate and clean up heavily loaded aqueous samples for the analysis of volatile polar organic compounds by means of direct aqueous injection-gas chromatography was studied. Recoveries for acetone, acetonitrile, acrolein, acrylonitrile, butanone, 1,4-dioxane, ethyl acetate, and 3-pentanone were in the range of 60.6 to 73.4% with relative standard deviations of 3.6 to 5.5%. The corresponding enrichment factors were in the order of 200. The recovery did not depend on the concentration in the studied range of 0.70 to 89 g/kg. The detection limits with the mass selective detector operating in the selected ion monitoring mode were in the order of 0.1 g/kg. The method was successfully applied to treated waste water from a pharmaceutical factory. The content of the above analytes in the real sample ranged from below 0.1 to ca. 83 g/kg.