AbstractIn grape berries (Vitis vinifera L.), sesquiterpenes are mainly accumulated as hydrocarbons in the epicuticular wax layer of grapes, whereas monoterpenes, which are predominantly present as alcohols, are glycosylated and are stored as glycosides in the vacuoles of grape berry cells. In this study, extensive analysis of grape berry hydrolysates by means of comprehensive two-dimensional gas chromatography–time-of-flight–mass spectrometry demonstrated that glycosylated sesquiterpene alcohols show very little structural diversity when compared to the sesquiterpene hydrocarbon fraction in the cuticle and are glycosylated to a rather low extent when compared to monoterpenols. Twenty-four enzymatically released terpenols were found in hydrolysates of the aromatic white wine variety Gewürztraminer (V. vinifera subsp. vinifera) after previous solid-phase extraction and headspace solid-phase microextraction. The detection of only three sesquiterpene alcohols, namely farnesol, nerolidol and drimenol, shows that most sesquiterpene hydrocarbons do not have a related hydroxylated structure in grapes. Nevertheless, the presence of the acyclic aglycone farnesol and nerolidol may be of importance for the wine aroma, since these structural isomers can be converted into numerous sesquiterpenes by nonenzymatic acid-catalyzed reactions during wine production. Grape-derived glycosidically bound sesquiterpene alcohols, therefore, represent, in addition to free sesquiterpene hydrocarbons, another pool of compounds that may influence the aroma profile of wines.