Sensory-directed fractionation of extracts prepared from raw and cooked asparagus (Asparagus officinalis L.), respectively, followed by LC-TOF-MS, LC-MS/MS, and 1D/2D-NMR experiments revealed the chemical structures of nine bitter tasting mono- and bidesmotic saponins as well as the previously not reported 1,2-dithiolan-4-carboxylic acid 6-D-α/β-glucopyranose ester exhibiting an interesting buttery mouth-coating effect. Sensory studies showed that the orosensation imparted by this sulfur compound was reminiscent to that of melting butter and revealed an orosensory recognition threshold of 276.8 μmol/L.