Metabolites during Baijiu fermentation process are closely related to its unique style characteristics. Characteristics and succession of metabolites for Laobaigan Baijiu during its fermentation process have not been comprehensively analyzed. The metabolites of fermented grains during the fermentation process of Laobaigan Baijiu were identified by ultra-high performance liquid chromatography-tandem mass spectrometer. The differential metabolites were screened by principal component analysis and significant difference analysis, and then the possible metabolic pathways of these differential metabolites were annotated by KEGG database. Results showed that 2 157 metabolites were detected in 9 samples of fermented grains with different fermentation time, of which 172 were extremely significant different metabolites (VIP>2, P<0.01, |log2 (FC)|>0.1). In different stages of fermentation, the expression levels of various metabolites were different. In the early stage of fermentation (0-8 d), there were the most differential metabolites, with 128 extremely significant differential metabolites (P<0.01). The metabolism of amino acids, peptides and their analogs, lipids, heterocyclic compounds, carbohydrates, and carbohydrate conjugates was significantly up-regulated. In the middle stage (8-17 d), there were 22 metabolites with extremely significant differences (P<0.01). The metabolism of amino acids, peptides and their analogs was significantly up-regulated (8-14 d), and lipids metabolism was up-regulated first and then down-regulated, while flavonoids metabolism was down-regulated first and then up-regulated. In the later stage (17-36 d), there were 33 metabolites with extremely significant differences, and the metabolism of amino acids, peptides and their analogs, and lipids was up-regulated first and then down-regulated. In addition, 104 metabolic pathways were annotated by KEGG database, and the metabolic network diagram was depicted accordingly. In different stages of fermentation, some metabolic pathways such as carbohydrate metabolism, lipid metabolism, flavonoid metabolism, and amino acid metabolism became more active mainly in the early stage of fermentation (P<0.05), flavonoid metabolism was more active in the middle stage of fermentation (P<0.05), lipid metabolism and amino acid metabolism were more vigorous in the late stage of fermentation (P<0.05). Eighteen metabolites, such as serine, glutamine, and aspartate semialdehyde, showed significant differences in several fermentation stages, and they annotated galactose metabolism, glycine, serine and threonine metabolism, arginine and proline metabolism, phenylalanine, tyrosine and tryptophan biosynthesis, and glycerophosphate metabolism, which may be the potential pathways to produce flavor compounds. Based on metabonomics technology, the characteristics and succession of metabolites during the fermentation process of Laobaigan Baijiu were revealed, which could provide a theoretical basis for analyzing the flavor metabolism mechanism during the fermentation process of Laobaigan Baijiu.