Determination of the botanical origin of raw spirit used for alcoholic beverage production is of great importance for rectifying units, control laboratories, and proper product labeling. Raw spirit samples (138) produced from rye, corn, and potato were analyzed using a solid phase microextraction-mass spectrometry (SPME-MS) method, which involved volatiles preconcentration by SPME with subsequent volatile fraction characterization by MS without particular compounds separation by GC. Obtained data were treated using principal component analysis and linear discriminant analysis (LDA) to test the possibility of sample classification. SPME sampling conditions allowed rapid extraction in 2 min at 50 °C using a carboxen/divinylbenzene/polydimethylsiloxane fiber, followed by rapid MS analysis. Use of LDA made possible the classification of raw spirits based on the material they were produced from. The classification ability of the developed SPME-MS method was 100%, whereas its prediction ability was 96%.