The aroma of the three different classes of Sherry vinegar was evaluated by gas chromatography/ mass spectrometry (GC-MS) and gas chromatography/olfactometry (GC-O). GC-O was employed to identify substances responsible for aromatic notes associated with the selected descriptors of the typical aroma of Sherry vinegar and odor activity values (OAV) calculated to measure the single impact effect of different compounds selected by GC-O. Diacetyl, isoamyl acetate, ethyl isobutyrate, isovaleric acid, sotolon, and ethyl acetate reached high OAVs, turning out to be characteristic odor active compounds in Sherry vinegars. A total of 58 compounds were quantified, among them, 7 had not been previously reported in Sherry wine vinegars: ethyl 2-methylbutyrate, ethyl heptanoate, ethyl furoate, and ethyl benzoate, acetophenone, nonanoic acid, and sotolon. Linear discriminant analysis (LDA) reveals that using aroma compounds as variables, we can classify Sherry vinegars with 100% correct scores as different from red wine vinegars.