Strong-flavor-type Baijiu, represented by Wuliangye—a renowned traditional Chinese alcoholic beverage brewed from five grains (sorghum, rice, glutinous rice, wheat, and corn)—is widely consumed and appreciated for its balanced taste and potential health benefits. While the volatile flavor compounds of Baijiu have been well studied, its bioactive components and their underlying mechanisms remain insufficiently explored. In this study, widely targeted metabolomics techniques were innovatively employed, and 2128 compounds were identified from 10 Wuliangye samples, of which 445 were predicted to constitute potential bioactive substances. Network pharmacology analysis further identified four key compounds, namely the four potential bioactive small molecules (fisetin, luteolin, norartocarpetin, and scutellarein), along with ten core targets that were key protein targets interacting with these compounds (SRC, PIK3R1, PTGS1, AKR1B1, STAT3, CYP3A4, ESR1, PIK3CA, PIK3CB, and ALOX15). GO and KEGG enrichment analyses indicated that these targets participated in diverse biological processes, while DO analysis revealed potential associations between these targets and specific diseases. Additionally, molecular docking confirmed the binding patterns between the identified compounds and their targets. Collectively, this study provides systematic chemical information and theoretical screening results for identifying potential bioactive components in strong-flavor-type Baijiu, which may facilitate further studies of their biological functions.