The high-throughput sequencing technology was used to identify the microorganisms during the brewing process of Laobaigan-flavor Baijiu, and the available data were analyzed for α and β diversity. 310 bacterial genera and 59 fungal genera were obtained, including the dominant bacterial genera of Lactobacillus, Pediococcus and Weissella, and the dominant fungal genera of Saccharomycopsis, Issatchenkia, Rhizopus, Trichosporon, Candida and Aspergillus. Headspace solid phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) was used to detect and quantify the microconsituents in fermented grains, and the heatmap of the detected trace components was drawn. The results showed that 0-3d had a small peak of the increase of microconsituents, most of the microconsituents were increased with little change of species during 3-14d, and a large number of esters were synthesized during 14-21d, and the growth rate of microconsituents were gradually decreased during 21-30d. Lactobacillus, Bacillus, Fusarium, Staphylococcus and Thelebolus, which had certain contribution to microconsituents, were gain during Laobaigan-flavor Baijiu brewing via Spearman correlation coefficient analysis of microbes and microconsituents or microbes and microbes.