Chinese sweet rice wines (CSRW) are traditional, regionally distinct alcoholic beverages that are generally brewed with glutinous rice and fermentation starters. This study aimed to characterize microbial communities and volatile compounds of CSRW starters and explore correlations between them. The major volatiles in starters include 1-heptanol, 1-octanol, 2-nonanol, phenylethyl alcohol, 2-nonanone, acetophenone, and benzaldehyde. Microbiological analysis based on high-throughput sequencing (HTS) technology demonstrated that starter bacterial communities are dominated by Weissella, Pediococcus, and Lactobacillus, while Saccharomycopsis and Rhizopus predominate in fungal communities. Carbohydrate and amino acid metabolism are the most active metabolic pathways in starters. Spearman correlation analysis revealed that 15 important volatile compounds including alcohols, acids, aldehydes and esters were significantly positively correlated with nine microbial genera (|r| > 0.7, p < 0.05), including five bacterial genera (i.e., Weissella, Pediococcus, Lactobacillus, Bacillus, and Nocardiopsis) and four fungal genera (i.e., Saccharomycopsis, Rhizopus, Wickerhamomyces, and Cyberlindnera), spanning 19 distinct relationships and these microorganisms were considered the core functional microorganisms in CSRW starters. The most important positive correlations detected between phenylethyl alcohol and Weissella or Saccharomycopsis and between 2-nonanol and Pediococcus. This study can serve as a reference to guide the development of defined starter cultures for improving the aromatic quality of CSRW.