The volatile composition of 26 premium quality vinegars belonging to three different protected geographical indications (traditional balsamic vinegar of Modena, balsamic vinegar of Modena, and sherry vinegar) has been characterized by means of a solid-phase extraction (SPE) gas chromatography-mass spectrometry GC-MS method. Among the about 90 quantified compounds, short-chain fatty acids, furanic compounds, enolic derivatives, and some esters were found to discriminate the samples as a consequence of differences in the extent of Maillard reactions, presence of alcoholic fermentation, or duration of wood aging.