Sensory-directed fractionation of traditional balsamic vinegar of Modena (TBV) led to the identification of the sweet-bitter tasting hexose acetates 6-O-acetyl-α/β-d-glucopyranose and 1-O-acetyl-β-d-fructopyranose as well as the previously unknown sweetness modulator 5-acetoxymethyl-2-furaldehyde. Taste re-engineering experiments and sensory time-intensity studies confirmed 5-acetoxymethyl-2-furaldehyde to contribute to the typical long-lasting sweet taste quality of TBV. Moreover, the response of the sweet taste receptor to this furaldehyde was verified by means of a functional hTAS1R2/hTAS1R3 receptor assay. Quantitative analysis of a total of 59 nonvolatile sensometabolites and taste modulators revealed higher concentrations of the sweet-modulating 5-acetoxymethyl-2-furaldehyde, nonvolatile organic acids and polyphenols such as wood-derived ellagitannins, and lower concentrations of acetic acid in the premium quality TBV when compared to balsamic vinegar of Modena (BV). Quantitative monitoring of sensometabolites throughout TBV manufacturing, followed by agglomerative hierarchical clustering and sensomics heatmapping, gave molecular insights into the taste alterations occurring during TBV maturation.