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The microbial community diversity in huangjiu (yellow rice wine) vinasse during spontaneous fermentation into Xiangzao was analyzed by high-throughput sequencing. It turned out that the bacterial and fungal diversity was abundant. During the whole fermentation process, Proteobacteria was the dominant bacterial phylum, whose relative abundance ranged from 71.26% to 75.27%. The relative abundance of Firmicutes was 16.09% in the initial stage of fermentation and showed a downward trend in the middle and late stages. The dominant bacterial genera were Aquabacterium and Brevundimonas. The relative abundance of Aquabacterium was 22.48% at the beginning of fermentation, increased to 24.94% at the middle, and decreased to 21.29% at the end. Bacillus and Lactobacillus were also found during fermentation. The dominant phylum of fungi was Ascomycota, and its relative abundance decreased from 63.46% at the beginning of fermentation to 51.68% at the end. The dominant genus of fungi was Pichia, and its relative abundance ranged from 6.58% to 13.79%. Additionally, the relative abundance of Tausonia and Mortierella was above 3%. To sum up, the microbial community diversity is abundant during the spontaneous fermentation of huangjiu vinasse, and the fermentation process has a significant impact on the relative abundance of microorganisms.