Abstract: Saccharification and fermentation are essential processes in the production of Baijiu and directly determine the yield of Baijiu. Eurotium critatum has a synergistic glycation effect, and the addition of Eurotium critatum affects the Daqu microbial distribution and flavor of Baijiu. In this paper, the main biochemical indexes, microflora and fermented Baijiu flavor components of Daqu added with Eurotium cristatum and traditional Daqu were compared, and the effects of Eurotium cristatum on Daqu quality and Baijiu flavor were analyzed. The results showed that the added Eurotium critatum culture had higher esterification, fermentability and saccharification power compared with the traditional Daqu, which increased by 6.70%, 125.0% and 28.35%, respectively. The functional microbial species and quantity were significantly increased, with 6.68, 2.12, 2.25 and 6.02 times more bacteria, yeast, mold and lactic acid bacteria, respectively, than those in the traditional Daqu. The types of major flavor substances and the contents of ethyl lactate and ligustrazine were significantly increased in the Baijiu fermented with the addition of Eurotium critatum compared with those fermented with traditional Daqu, which improved the quality of the Baijiu.