Baijiu, one of the world’s oldest distilled liquors, is widely consumed globally and has gained increasing popularity in East Asia. However, a comprehensive understanding of the underlying principles behind this traditional liquor product remains elusive. Currently, Baijiu is facing the industrial challenge of modernization and standardization, particularly in terms of food quality, safety, and sustainability. The current study selected a Lactobacillus brevis strain based on experiments conducted to assess its environmental tolerance, enzyme activity, and fermentation performance, and highlight its exceptional fermentation characteristics. The subsequent analysis focused on examining the effects of fortifying the fermentation process of L.brevis on key microbiotas, physicochemical parameters, and volatile profiles. The qPCR results revealed that the inoculated L. brevis strategically influenced the the composition of the dominant microbial communities by promoting mutual exclusion, ultimately leading to improved controllability of the fermentation process. Moreover, the metabolism of the inoculated L. brevis provided more compounds for the formation of flavor profiles during fermentation (the content of ethyl acetate was increased to 57.76 mg/kg), leading to a reduction in fermentation time (from 28 d to 21 d). These findings indicate promising potential for the application of the indigenous strain in Baijiu production.