A solid-phase microextraction (SMPE) method coupled to a gas chromatography-mass spectrometry analysis was optimized to analyze the pentafluorobenzyl bromide (PFBBr) derivatives of the volatile thiols 4-methyl-4-mercapto-2-pentanone (4MMP), 3-mercaptohexyl acetate (3MHA) and 3-mercaptohexanol (3MH) in wine. This method used deuterated analogue compounds as internal standards. It allowed us to significantly reduce the matrix effect, resulted in good repeatability for all the compounds (RDS<9.5% for 4MMP; <6% for 3MH and <4.1% for 3MHA) with limits of detection below their odour thresholds. The method was validated using white, rosé and red wines. When applied to analyze different wines, quantities closed to the odour threshold were determined.