An alternative sorptive microextraction method for the determination of five halogenated anisoles in water and wine matrices is proposed. Analytes were concentrated in an inexpensive and disposable piece of bulk polydimethylsiloxane (PDMS), desorbed with a small volume of organic solvent, and determined by gas chromatography with electron–capture detection (GC–ECD) or tandem mass spectrometry (GC–MS/MS). The influence of several factors on the efficiency of extraction and desorption steps was investigated in detail and the observed behaviour justified on the basis of thermodynamics and kinetics of the solid-phase microextraction technique. Under optimised conditions, analytes were first extracted in the headspace (HS) mode, at room temperature, for 2.5h and then desorbed with 1mL of n-pentane. This extract was further evaporated to 50μL. The overall extraction yield of the procedure ranged from 40 to 55% and the limits of quantification remained between 0.5 and 20ngL −1 , depending on the compound considered and the detection technique. Precision and linearity of the method were excellent for all species with both GC–ECD and GC–MS/MS detection. Matrix effects were evaluated with different water and wine samples; moreover, the suitability of the PDMS sorbent for storage of analytes, under different conditions, was demonstrated.