Abstract: To clarify the aroma-producing characteristics of Bacillus licheniformis in high-temperature Daqu of sauce-flavor Baijiu and its contribution to Baijiu flavor formation, this study isolated and purified 16 strains of B. licheniformis from high-temperature Daqu. Using programmed temperature solid-state fermentation combined with artificial sensory evaluation, as well as headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography–mass spectrometry (GC-MS), the relationship between metabolic profiles and sensory attributes of different strains of the same species was systematically analyzed. The results showed that the flavor characteristics of solid-state fermentation products from different strains could be classified into five categories: roasted/nutty-fatty aroma, douchi aroma, sulfurous notes, soy sauce/fermented paste aroma, and fruity-acidic aroma. A total of 198 volatile compounds were identified through volatile component analysis. Pyrazines were dominant in all strain types, while the composition of other volatile compounds showed distinct differences: Aldehydes, ketones, and alcohols were more abundant in strains with roasted/nutty-fatty aroma, douchi aroma, sulfurous notes; aldehydes, acids, and alcohols were higher in soy sauce/fermented paste aroma strains; and acids and ketones were predominant in fruity-acidic aroma strains. Key differential aroma components were further screened by orthogonal partial least squares-discriminant analysis (OPLS-DA) with a variable importance in projection (VIP) value>1.0, and combined with a relative odor activity value (ROAV)>1.0. Five substances were ultimately identified as crucial for discriminating the aroma profiles of different sensory categories of B. licheniformis: 4-methoxyphenol (a key common component of roasted/nutty-fatty aroma, douchi aroma, and soy sauce/fermented paste aroma strains), isovaleric acid (a key common component of douchi aroma and fruity-acidic aroma strains), 2-octanone (a key component of fruity-acidic aroma strains), 2,3,5-trimethylpyrazine (a key component of roasted/nutty-fatty aroma, douchi aroma, and sulfurous notes strains), and 2,3,5,6-tetramethylpyrazine (a key component of soy sauce/fermented paste aroma strains).