The enantiomeric distribution of 3-mercaptohexan-1-ol (3MH) and 3-mercaptohexyl acetate (3MHA) in Vitis vinifera wines was determined by combining two techniques: specific purification of volatile thiols from the wines using p-hydroxymercuribenzoate and separation of the chiral molecules by gas-phase chromatography on a cyclodextrin capillary column. The R and S enantiomer ratios of these two thiols in dry white Sauvignon blanc and Semillon wines are approximately 30:70 for A3MH and 50:50 for 3MH. However, in sweet white wines made from grapes affected by "noble rot" due to the development of Botrytis cinerea on ripe grapes, the proportion of the R and S forms of 3MH is in the vicinity of 30:70. During alcoholic fermentation, a change in the ratio of the two enantiomers of 3MH in dry white wines was observed. At the beginning of fermentation (around density 1.08), the S form represented over 60%; then, at lower density, as fermentation proceeded, the enatiomeric ratio approached 50:50. The ratio of the two 3MHA enantiomers remained constant throughout fermentation. On the contrary, the distribution of the two 3MH enantiomers changed very little during fermentation of the botrytized sweet wines. The perception thresholds for the R and S forms of 3MH in hydroalcoholic model solution are similar (50 and 60 ng/L). These two enantiomers have quite different aromas: The R form is fruitier, with a zesty aroma reminiscent of grapefruit, while the S form smells more of passion fruit. The perception thresholds of the R and S enantiomers of 3MHA are slightly different (9 and 2.5 ng/L). The less odoriferous R form is reminiscent of passion fruit, while the S form has a more herbaceous odor of boxwood.