Hongqu rice wine was brewed with glutinous rice as raw material and Hongqu as starter. Monascus and Saccharomyces cerevisiae were the core microorganisms in the brewing system. In this paper， using glutinous rice as the fermentation substrate， Monascus purpureus， Monascus ruber and Monascus kaoliang were combined with S. cerevisiae to study the effects of different combinations and fermentation modes (simultaneous fermentation and sequential fermentation) on the production of volatile components. A total of 89 volatile flavor compounds were identified from fermented rice wine based on headspace solid phase microextraction-gas chromatography mass spectrometry (HS-SPME-GC-MS). Heat map analysis showed that the combined fermentation of Monascus and S. cerevisiae produced more aroma substances than the pure fermentation of Monascus， and the sequential fermentation produced more aroma substances than the simultaneous fermentation， especially the sequential fermentation of M. purpureus， M. ruber and S. cerevisiae. According to the principal component analysis of volatile flavor components of different Monascus and S. cerevisiae combined fermentation， M. purpureus and M. ruber and S. cerevisiae will produce more volatile flavor components under the sequential fermentation mode， and their flavor compositions were close to each other. Through the analysis of the content difference of volatile flavor components， isobutanol， 1-heptanol， (3Z)-3-nonene-1-ol， 2-tetradecanol， (Z)-5-octene-1-ol， decanal， ethyl caproate， ethyl decanoate， 9-decenoate， ethyl phenylacetate， ethyl acetate， 1，2-dimethoxy-4-vinyl benzene， acridine were the characteristic volatile flavor substances in the combined fermentation products of Monascus and S. cerevisiae. The results of this study could provide a theoretical basis for the improvement of flavor quality and quality control in the industrial production of Hongqu rice wine.