Effective monitoring and control of water contamination resulting from underground coal gasification requires methods of analysis for contaminants that can be used at several levels of sophistication. These range from simple groundwater contaminant monitoring methodologies that can be used by personnel with minimal skills, through gas chromatographic/mass spectrometric identification of specific organic compounds present at very low levels. Frequently, the most desirable approach is one that first divides the contaminants into classes on the basis of their general chemical characteristics and/or biogeochemical behavior followed by the analysis of the total contaminants in each of these classes. Each fraction should be directly analyzable, so that none is determined by difference. Provision should be made to preserve each sample for further, more sophisticated analysis or bioassay, if required. This paper describes a separation and analysis scheme recommended for use by the Laramie Energy Technology Center, which fulfills the criteria outlined above. Based upon solvent separation with methylene chloride, it divides water contaminants from underground coal gasification among hydrophilic, organophilic, and insoluble fractions. The hydrophilic and organophilic portions may be further subdivided among acid, base, and neutral fractions. The insoluble fractions, initially present as suspended or colloidal material, may be retained for further characterization, such as by pyrolysis gas chromatography. This paper describes the separation scheme, as well as the characterization of the hydrophilic and organophilic acid, base, and neutral fractions by dissolved organic carbon analysis and gas chromatography.