The present study was to analyze the water dynamics of Tricholoma matsutake Singer during hot air drying by low-field nuclear magnetic resonance (LF-NMR) and magnetic resonance imaging (MRI), and to investigate the volatile compounds in the pileus, upper stipe and lower stipe of fresh and dried Tricholoma matsutake Singer by headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) and headspace solid-phase microextraction-gas chromatography–mass spectrometry (HS-SPME-GC–MS). Fresh samples were dried at 60 °C for 12 h. With the T2i relaxation times decreasing, the water migrated from the inner toward the periphery and then expelled during drying. The characteristic volatiles fingerprints of different parts of fresh and dried samples were established by HS-GC-IMS. The significant differences in volatile compounds were observed among different parts of the fresh sample and C8 compounds (70%–97%) were the principal components. After drying, the concentration of C8 compounds dramatically decreased and some volatile compounds (hexanal, heptanal, 2(5H)-furanone, acetophenone, nonanal, benzeneacetaldehyde) were formed. Thus, hot air treatment affected the volatile compounds in Tricholoma matsutake Singer.