Thermophilic bacteria play an important role in aroma formation during pile-fermentation process of dark tea. With the aim to reveal the impact of thermophilic bacteria on volatile compounds in dark tea, Bacillus licheniformis (thermophilic bacteria) were inoculated into sun-dried green tea for spontaneous fermentation. In this study, headspace solid phase microextraction combined to gas chromatography mass spectrometry (HS-SPME-GC-MS), odor activity value (OAV), principal component analysis (PCA) and orthogonal partial least squares discrimination analysis (OPLS-DA) were employed to investigated the characteristics of volatile compounds during thermophilic bacteria pile-fermentation. According to HS-SPME-GC-MS, a total of 64 volatile compounds were identified. PCA revealed that tea samples could be clearly discriminated from each other. Furthermore, sulcatone, hexanoic acid, linalool, 2-methyl-trans-decalin, myrtenal, and α-ionone were found to play an important role in discrimination of tea samples, based on OPLS-DA. In addition, the OAV could effectively characterize the aroma contribution of volatile compounds during thermophilic bacteria pile-fermentation, and (Z)-linalool oxide (furanoid), α-ionone, (E)-2-nonenal, and linalool were the critical volatile compounds of aroma quality in dark tea. This study provides insight into volatile compounds characteristics during thermophilic bacteria pile-fermentation in dark tea.