Dissolved organic carbon (DOC) plays a key role in determining the environmental fate of semivolatile organic environmental contaminants. The goal of the present study was to develop a method using commercially available hardware to rapidly characterize the sorption properties of DOC in water samples. The resulting method uses negligible-depletion direct immersion solid-phase microextraction (SPME) and gas chromatography-mass spectrometry. Its performance was evaluated using Nordic reference fulvic acid and 40 priority environmental contaminants that cover a wide range of physicochemical properties. Two SPME fibers had to be used to cope with the span of properties, 1 coated with polydimethylsiloxane and 1 coated with polystyrene divinylbenzene polydimethylsiloxane, for nonpolar and semipolar contaminants, respectively. The measured DOC-water distribution constants showed reasonably good reproducibility (standard deviation ≤ 0.32) and good correlation (R(2)  = 0.80) with log octanol-water partition coefficients for nonpolar persistent organic pollutants. The sample pretreatment is limited to filtration, and the method is easy to adjust to different DOC concentrations. These experiments also utilized the latest SPME automation that largely decreases total cycle time (to 20 min or shorter) and increases sample throughput, which is advantageous in cases when many samples of DOC must be characterized or when the determinations must be performed quickly, for example, to avoid precipitation, aggregation, and other changes of DOC structure and properties. The data generated by this method are valuable as a basis for transport and fate modeling studies.