Daqu has gained wide attention because it is an essential source of microorganisms and flavor in baijiu production. In this study, HS-SPME combined with GC-MS/O was used to analyze the volatile flavor components of Strong aroma baijiu Daqu. DI-GC-O was used to choose the best extraction fiber to extract the representative overall aroma profile of Daqu. A total of 139 compounds were identified in the six different maturity stages of Daqu, and these compounds are of different types and concentrations. HS-SPME combined with GC-MS/O was used to analyze the aroma active substances in the finished Daqu, and a total of 43 aroma compounds were identified. The OAVs of 21 aromatic compounds were calculated based on the quantitative analysis results of MHS-SPME. Eighteen compounds with OAVs ≥ 1 made significant contributions to the overall aroma of Daqu, including guaiacol, 4-ethyl-2-methoxy phenol, 2-ethyl-3,5-dimethylpyrazine, etc.