The brewing of Chinese Baijiu is a microbial community fermentation system, in which there is a close and complex relationship between microorganisms and flavor quality, but the specific deep-seated mechanism still needs to be explored and interpreted continuously so far. In this review, Maotai flavor Baijiu was briefly introduced, and the microorganisms mainly affected by flavor substances, the main components of flavor substances, the factors affecting flavor formation and the application ways of functional microorganisms in Maotai flavor Baijiu were summarized. It provides a deeper understanding for the research of others flavor Baijiu.