This paper presents the application of comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry (GCxGC/TOFMS) using the longitudinal modulated cryogenic system (LMCS) device, to the aroma analysis of spirit samples. The volatile organic compounds present in samples of a Brazilian cane sugar spirit were collected by using a solid-phase microextraction (SIPME) method. Other samples studied included gin, vodka, whiskey, tequila and flavoured liqueurs. In this study GCxGC/TOFMS with a bi-dimensional non-polar - polar phase column set comprising of a first dimension BPX5 primary column and a second dimension BP20 second column enabled the tentative identification of 95 compounds in cachaca. In excess of 200 compounds were found amongst group of samples that were analysed. The results, presented as peak apex plots, showed that groups of compounds were present in well-defined regions of the 2D separation space in each beverage, making it possible to recognise the differences and similarities among the spirit samples.