A simple and sensitive method was developed and validated to simultaneously separate and determine the 2‐Methoxy‐3,5‐dimethylpyrazine, 2‐Isopropyl‐3‐methoxypyrazine, guaiacol, 2‐Isobutyl‐3‐methoxypyrazine, 2‐Methylisoborneol, geosmin, 2,4,6‐Trichloroanisole, 2,3,4,6‐Tetrachloroanisole, 2,4,6‐Tribromoanisole and Pentachloroanisole in cork stoppers via headspace solid‐phase microextraction (HS‐SPME) coupled with gas chromatography tandem mass spectrometry (GC–MS/MS). The influence of the fibre coating used, the extraction times and temperatures, the sodium chloride additions and the desorption temperatures were investigated. Once done, the optimial HS‐SPME conditions established were divinylbenzene/carboxenpolydimethylsiloxane/polydimethylsiloxane (DVB/CAR/PDMS) fibres, a 50°C extraction temperature, 60‐min extraction time, an ionic strength of 3‐g sodium chlorid and a 290°C desorption temperature. The method showed a good linearity (R2 ≥ 0.994) within the tested range (from 0.1 to 50 ng L−1) for all the compounds. Using TCA‐d10 and MIB‐d3 as internal standards the precision, expressed as repeatability and reproducibility RSD, was <10% in both. Note that the limits of quantifications (LOQs) are below the sensory threshold levels for such compounds in water and wine. Good recoveries were obtained for cork macerates (from 100.4% to 126%) and when compared with other reported methods using HS‐SPME in water and cork stopper samples, the present method had more analytes with the lowest limit of detection for most of the targeted compounds, along with good precision and recovery.