The microbiota in traditional solid-state fermentation is a complex microbiota that plays a key role in the production of feed, fuel, food and pharmaceutical products. The function of microbiota is an important factor dictating the quantity and quality of products. Core functional species play key metabolic roles in the microbiota, and their disappearance could result in the abnormal fermentation process. In this work, we combined Baijiu production and laboratory experiments to explore the keystone microbes and their metabolites. We found the deletion of core functional microbe resulted in the loss of multiple metabolites involved many alcohols and acids. In the traditional Baijiu production, the absence or appearance of Schizosaccharomyces pombe caused the content divergence in 227 flavor-related metabolites, especially in ethanol, butanol and pentanoic acid between abnormal and normal group (each content > 1 mg/kg and the content ratio of normal/abnormal group > 2). Schi. pombe increased the expression level of related genes involving alcohol dehydrogenase (ADH), acyl-CoA oxidase (ACOX) and trans-2-enoyl-CoA reductase (TER). Moreover, in the verification experiment of laboratory, the absence or appearance of Schizosaccharomyces pombe C-11 caused the content divergence in 136 flavor-related metabolites, especially in ethanol, butanol and pentanoic acid between Sp- and Sp+ group (each content > 1 mg/kg and the content ratio of Sp+/Sp- group > 2). Our results identified specific member that were essential for the function of fermentation microbiota. This study also suggests species deletions from fermentation microbiota and synthetic consortium could be a useful approach to illustrate relevant microbe-metabolites association and defining metabolic roles in the traditional solid-state fermentation.