The present contribution describes a research work focused on the elucidation of the composition of the headspace of Marsala wine. Four sample-types, of different ageing ("fine", "superiore secco", "superiore riserva", "vergine") were subjected to headspace solid-phase microextraction-comprehensive 2D GC analysis. At the outlet of the second GC dimension, the eluting analytes were split between a flame ionisation detector (for relative quantification purposes) and a rapid-scanning quadrupole mass spectrometer (for compound identification). Over 500 peaks were detected in each application, with a total of 128 compounds tentatively-identified considering the four sample types (mainly esters, alcohols, ketones, and aldehydes). The results attained open a door on the highly complex nature of the Marsala headspace; furthermore, they also demonstrated that the use of one-dimensional GC technologies, for the untargeted analysis of complex aroma profiles (e.g., dessert wines), is often too much of an analytical challenge.