As a traditional Chinese rice wine, Hong Qu glutinous rice wine (HQW) is popular among consumers due to its unique flavor. However, its quality changes during fermentation, and the potential relationships between flavor and microbes have not been systematically researched. In this work, physicochemical properties (pH, total sugar, alcohol, amino acid nitrogen), flavor compounds (organic acids, free amino acids, and volatile compounds), and microbial communities were investigated. The results revealed that Pantoea, Lactiplantibacillus, Lactobacillus, Leuconostoc, and Weissella predominated the bacterial genera, and Monascus was the predominant fungal genus. Organic acids, free amino acids, and key volatile compounds (esters and alcohols) significantly increased during fermentation. The correlations analysis showed that Lactiplantibacillus was closely associated with flavor compounds formation. This study deepens our understanding of the roles of microorganisms in flavor formation on traditional HQW fermentation.