This aim of this work was to identify the odorant compounds responsible for the typical sensory descriptors attributed to freshly distilled Cognac spirits, not matured in barrels. Panelists were first selected and trained for gas chromatography-olfactometry. Among the 150 volatile compounds identified by gas chromatography-mass spectrometry analysis, only 34 are mainly responsible for the odors detected in the spirits. The "butter" descriptor is explained by the presence of diacetyl, the "hay" descriptor by nerolidol, the "grass" descriptor mainly by Z-3-hexen-1-ol, but also by other compounds, the "pear" and "banana" descriptors by 2- and 3-methylbutyl acetates, the "rose" descriptor by 2-phenylethyl acetate, and the "lime tree" descriptor by linalool. This study demonstrated that many odorant molecules are already present in freshly distilled Cognac, thereby giving the spirit its specific aroma.