Wines are complex matrices famous for their pleasant aroma and exceptional flavor. Baijiu (white wine) is a traditional Chinese liquor with a soft mouthfeel, fragrant taste, and long-lasting aftertaste. Baijiu is distilled from sorghum and wheat via solid fermentation. As in wines, the microbial ecosystem of Baijiu is a key decisive factor influencing aroma and consumer preferences. Microbial diversity in Baijiu has been intensively investigated. It is important to note that probiotics are a mixture of bacteria and yeast primarily intended to improve health. Our study aimed to characterize the microbial ecosystem of Zaopei Baijiu Daqu (ZBD) starter cultures for specific microbes with probiotic properties. The DNA samples of ZBD starters were analyzed using a metagenomic 16S rRNA approach to characterize the bacterial and ITS for fungal diversity. Weissella cibaria was the most dominant species in the bacterial community, while Saccharomycopsis fibuligera was the most abundant fungal species. Furthermore, functional prediction analysis identified unique pathways associated with microbial diversity relevant to functional innovation. These associated pathways include fermentation, amino acid metabolism, carbohydrate metabolism, energy metabolism, and membrane transport. This study identified beneficial microbes in the starter culture, opening a path for further in-depth analysis of those microbes by isolating and evaluating them for a valuable role in in vitro and in vivo studies.