Enjoying a glass of spirits can be one of the delights of life. While it is well known that their taste improves during barrel aging, the molecular explanations of this phenomenon remain largely unknown. The present work aimed at searching for taste-active compounds formed in spirits during aging. An untargeted metabolomic approach using HRMS was applied on "eau-de-vie" of cognac. A fractionation protocol was then performed on brandies to isolate a targeted compound. By using HRMS and NMR, its structure was elucidated for the first time. This new ellagitannin, called brandy tannin A, considerably increased the sweetness of spirits at 2 mg/L. After development of an LC-HRMS quantitation method, it was assayed in various spirits and was detected mainly in cognacs up to 7 mg/L. These findings demonstrate the sensory contribution of this compound and more generally the relevance of combining metabolomics and separative techniques to purify new taste-active compounds.