The objective of this study was to develop and apply a procedure to determine products of the petroleum industry in aqueous samples using headspace SPME with a fiber for sampling and GC–FID for anal- ysis. Parameters of extraction (time, temperature, agitation rate, con- tent of salt), and the time and temperature of desorption in the gas chromatograph injector were selected. The procedure was validated and applied to analyze water contaminated by unleaded petrol and water used to extinguish a simulated fire.