Saccharification fermentation is very important technics for Chinese baijiu, which effects its yield and flavor. Eurotium cristatum was been found the ability of saccharification, but has not been applied to the saccharification fermentation in Chinese baijiu. In this study, E. cristatum was added to the mold culture for the co‐fermentation of Wuliangye liquor to verify whether it enhanced the saccharification efficiency. Starch from mold culture was analyzed to infer the effect. Microorganisms in the mold culture and liquor flavor substances were also evaluated. Results showed that reducing sugar in the fermented grains reached the maximum value of 40 g/100 g when 8 mL of E. cristatum suspension was added to 100 g of mold culture. Co‐fermentation using E. cristatum increased the amylose content, decreased the molecular weight, and formed irregular starch particles and an evident crystal structure of starch from the mold culture. These phenomena in starch molecules corresponded to the mechanism by which E. cristatum enhanced saccharification efficiency. What's more, E. cristatum also improved the growth of the original microorganisms in the mold culture, thereby benefitting the flavor of Wuliangye liquor. Therefore, it is scientific and significative for the application of E. cristatum in saccharification fermentation of Wuliangye liquor.This article is protected by copyright. All rights reserved