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The work we present in this article aims at optimizing and validating the assay technique based on SIDA-HSSPMEGC- MS/EI-SIM by means of intra-laboratory trials (NF V03-110 AFNOR 1998 and MA-F-AS1-06-PROVAL (OIV)) on several chloroanisoles (2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole, 2,3,4,5,6-pentachloroanisole) likely to contaminate wine by direct or indirect contact, in order to define the precise characteristics and limitations of the method. We showed this technique to be a specific, accurate, linear, and repeatable method. Moreover, seeing the increasing reliance on this type of approach in scientific research and industrial monitoring laboratories (ISO/TC87/GT10) to assess the quality of cork stoppers and because of the important quantity of 2,4,6-Trichloroanisole present in this kind of material, we deemed appropriate to carry out an inter-laboratory study (ISO 5725-1,2,3,4 and 5) of TCA assays on dilute alcohol soaks of corks using the same method. Our results should make it easier to understand and interpret assay results obtained in different laboratories using the same technique. * : Stable Isotope Dilution Assay - Headspace Solid Phase Microextraction - Gas Chromatography - Mass Spectrometry / Electron Impact / Selected Ion Monitoring.