Xiangzao brine is a special flavored food produced by the natural fermentation of Huangjiu lees. To clarify fermentation time on its quality, this study integrated flavoromics analysis, macro-genomics, and polypeptide omics to analyze the volatile flavor components, microbial species, and flavor peptide distributions of four groups of samples (XZ-1Y, XZ-2Y, XZ-3Y, and XZ-4Y) fermented for 1–4 years. The results showed that the samples fermented for 1 year had the highest contents of umami amino acids and umami peptides, and the samples fermented for 4 years had the highest contents of organic acids and fruity components. In addition, 42 volatile flavor components and 532 peptides were identified, including 393 umami taste peptides and only 37 bitter taste peptides. Correlation analysis showed that ethyl lactate and furfural were positively correlated with the abundance of Nocardioides and Stenotrophomonas, respectively. The abundance of Pseudomonas was positively correlated with four previously unreported umami peptides (FATPR, RELER, FNLERP, and RSSFLGQ) screened by molecular docking. This study provides a reference for the flavor metabolism regulation of Xiangzao brine.