Grape anthocyanins reacted with diacetyl, a secondary metabolite of microorganisms involved in winemaking, to form 10-acetyl-pyranoanthocyanins, a type of anthocyanin-derived pigments similar to other vitisin-type pyranoanthocyanins found in red wines. The structures of 10-acetyl-pyranomalvidin-3-β-O-glucoside and 10-acetyl-pyranopeonidin-3-β-O-glucoside were confirmed by spectroscopic methods (UV-vis, MS/MS, and NMR) after their synthesis and isolation. In contrast to other vitisin-type pyranoanthocyanins, the newly described 10-acetyl-pyranoanthocyanins exhibited differentiated color-related properties. They showed an important tendency to occur as colorless hemiacetals at C-10 under wine pH conditions, while co-occurrence of flavylium cation and quinoidal base yield a broad visible absorbance band around 510-520 nm. Moreover, they easily reacted with bisulfite in acidic aqueous solution (pH 2.0), but the expected bleaching was not observed. Bisulfite bonded to the carbonyl of 10-acetyl substituent instead the expected C-10 position of the pyranoanthocyanin core, thus giving rise to a red pigment hypsochromically shifted towards orangish nuances (maximum absorbances at 487-491 nm).