A HS-SPME method coupled to GC-MS was developed and applied for the qualitative and semiquantitative characterization of distilled gin volatile fraction. Sampling, chromatographic conditions, and method performances were evaluated, and the developed method was applied as a comparative study of some of the most popular commercial London Dry Gins and other gins with geographic denominations. During this study, 70 components of the gins' volatile fraction were isolated, tentatively identified or identified by reference compounds. They were mainly represented by mono- and sesquiterpenic compounds, which were quantitatively determined. The comparative study of London Dry Gins and gins with geographical indication permitted clear differentiation between the gins with geographical indication and one of the London Dry Gins tested.