A methodology based on microextraction, i.e., a one‐step extraction in which the ratio of solvent:wastewater ranged from 1:40 to 1:100, is described for the analysis of priority pollutant volatile aromatics, phthalates, polynuclear aromatics, and phenols. The use of this method for extracting relatively non‐polar analytes is justified from both a theoretical and a practical viewpoint. Results obtained during an EPA verification analysis of a variety of industrial process waters and effluents are discussed with respect to precision, percent recoveries of analytes, specific analytical problems encountered, and the potential for extending this approach to other compound classes.