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One of the most critical problems in the enological industry is associated with cork taint. The main compounds responsible for this off-flavour are some chloroanisoles: 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TECA) and pentachloroanisole (PCA). Headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-electron capture detection has been used for the direct determination of these chloroanisoles in wine samples. After the evaluation of some parameters (desorption conditions and salt addition) that affect extraction efficiency, a screening study of six types of fibres and five extraction temperatures was performed. Then, a Doehlert matrix including the exposure time, temperature and Vs (sample volume)/Vt (total volume) ratio as experimental factors was proposed. According to the results of this design and the kinetic profiles evaluated, an analytical procedure based on HS-SPME was optimised and validated. This method can be used for the simultaneous determination at the low ng/l level of all chloroanisoles involved in cork taint, and not only TCA, which is the only compound found in the literature when SPME is proposed as the analytical technique.