Data obtained with gas chromatography coupled with ion mobility spectrometry (GC-IMS) was explored to investigate the characteristics of volatile compounds from edible fungus, from Eucommia ulmoides Oliv. leaves (EUl) that served as growth medium, and from their fermentation products. A total of 162 signal peaks were found, of which 68 compounds were identified, including alcohols, aldehydes, ketones, acids, and esters. There were differences in the volatile constituents of the edible fungi. EUl also contained special volatile components. The volatile components in the fermentation product were different compared to the raw material, and the difference in composition and content of the characteristic compounds was also obvious. The best classification performance was obtained by principal component analysis (PCA) based on the signal intensity of the characteristic volatile compounds. The results clearly showed that the samples (edible fungi, EUl and fermentation products) in a relatively independent space would be well distinguished. This further illustrated that the composition and content of volatile components of EUl could be changed by different microbial strains through biofermentation technology. Combining the signal intensity of the flavor substance, the difference was also clearly observed. This result suggested that the flavor compounds fingerprint could be established by GC-IMS and PCA.