This study analyzed the succession patterns of a microbial community structure and key genera during the fermentation process of Daizhou Huangjiu (DZHJ). The results indicated that bacterial diversity decreased while fungal diversity increased in the traditional DZHJ fermentation process. Bacillota and Proteobacteria were the dominant bacterial phyla, whereas Ascomycota, Basidiomycota, and Mortierellomycota were the dominant fungal phyla. Weissella, Enterococcus, and Paucibacter were identified as the predominant bacterial genera, with Paucibacter being reported for the first time in Huangjiu research, marking it as a unique signature of DZHJ. Saccharomyces, Aspergillus, and Candida were the predominant fungal genera. Through Beta diversity analysis and LEfSe differential discriminant analysis, Enterococcus, Weissella, and Saccharomyces were confirmed as key differential genera. Additionally, Weissella and Saccharomyces showed significant negative correlations with the majority of bacteria and fungi, respectively. This study elucidates the brewing mechanism of DZHJ, providing a theoretical basis for its quality improvement.