The purpose of this paper was to characterize compounds from rye flour leaven, which is used for making prepare sour soup. It was found that for full characteristics of flavour compounds various isolation methods should be applied. The volatiles were isolated after 1, 2 and 3 days of spontaneous fermentation by using simultaneous steam distillation and extraction technique, static and also dynamic headspace techniques. Gas chromatography analyses were performed on capillary column of different polarities connected to flame ionization detector, electron capture detector, mass spectrometer and sniffing port. The organic acids were analyzed by high performance chromatography on HPX – 87H column and Dual Adsorbance Detector. Totally 26 compounds were identified: 6 acids, 7 alcohols, 4 aldehydes, 5 esters, 2 ketones, 1 hydrocarbon, 1 heterocyclic compound.