To identify volatile compounds with bitter and astringent taste in Baijiu (Chinese liquor), an extraction and isolation method was developed. The Baijiu sample separated into 4 fractions (A, B, C and D) by gradient vacuum distillation. The fraction B with strong astringency and bitterness was re-separated by semi-preparative-HPLC, and 10 sub-fractions were obtained. Each sub-fraction was extracted by pentane and diethyl ether，and the ether extraction phase was collected. Each organic phase was separated into two portions, wherein one was washed with pure water and evaporated by vacuum to remove solvent for taste dilution analysis (TDA), the other was concentrated to 250 μL under a gentle stream of nitrogen for GC-MS. The 4 sub-fractions B-8-II, B-2-II, B-3-II, and B-4-II had high TD factors of 128, 64, 32, and 8 for astringency, and 32, 16, 16 and 8 for bitterness, respectively, and 7 taste-active compounds were identified by GC-MS. Based on the reference compounds, 2-phenylethanol and ethyl lactate contributed astringency only, while furfural, 2-methypropanol, 3-methybutanol, 1-butanol, and 1-propanol gave both bitter and astringent taste. Among them, it was the first time to report the taste characteristics of 2-phenylethanol.