A method based on solvent extraction and GC-electron-capture detection analysis for the determination of 2,4,6-trichloroanisole (TCA) from cork has been evaluated and optimised. Our sample treatment consists of an extraction stage with pentane while the sample and solvent are kept in contact in a mechanical shaker (shake-flask extraction). Different extraction conditions have been tested in order to find the best compromise between efficiency and time of analysis. Different columns were evaluated for use in the concentration and purification step. A silica column was found to give the best performance in terms of recovery of TCA and repeatability. Pentane and mixtures of pentane-diethyl ether at different ratios were tested as eluting agents. It was found that 10 ml pentane allowed the recovery of retained TCA. Finally, the eluate was concentrated and injected into the chromatograph for TCA determination. The optimised chromatographic conditions enabled the quantification of TCA and 2,6-dichloroanisole, which was assayed as the internal standard. The shake-flask extraction method was compared with Soxhlet and ultrasound assisted extraction procedures using pentane as a solvent. Similar results were obtained for the shake-flask and Soxhlet extraction methods, while sonication gave significantly lower recoveries. The optimised shake-flask method was applied to determine the distribution of TCA in naturally contaminated cork bark.