The Slovak-Czech spirit distilled from Sorbus domestica was analyzed by GCxGC with headspace solid phase microextraction and liquid-liquid extraction. Two column combinations, nonpolar × medium-polar and polar × medium-polar were tested. The second column setup provided more exploited 2D separation space with better distribution of peaks in chromatogram. Effects of the first column on the elution order of γ-lactones, benzyl esters, and unsaturated aldehydes in the second separation were observed. More than 500 compounds were detected; nearly 100 were confirmed with standards.