In order to explore differences of volatile and non-volatile compounds between traditional and mechanical raw Baijiu of roasted-sesame-like aroma type Baijiu(Chinese liquor), the liquid-liquid microextraction (LLME) and hexamethyldisilazane (HMDS) derivatization coupled with gas chromatography-mass spectrometry (GC-MS) and other methods were employed. 94 kinds of compounds were detected both in traditional raw Baijiu and mechanical raw Baijiu. The results showed that the total concentrations of compounds in traditional raw Baijiu were higher than mechanical raw Baijiu. Except acids, phenols and lactones, the total concentrations of the other compounds in traditional raw Baijiu were higher than those in mechanical raw Baijiu. By comparing the concentrations of the components in the two crafts of Baijius, 12 compounds were significantly different, including 4-ethylphenol, 4-ethylguaiacol, 1,1,3-triethoxypropane, 2-hydroxybutyric acid, butyl lactate, 3-hydroxybutyric acid, 1-butanol, 2-furanmethanol, furfural, isoamyl butyrate, 2-phenylethyl butyrate, and 3-hydroxypropionic acid.