The relationship of polybasic acids and higher fatty acid content with sensory quality of tobacco raw materials from the different tobacco growing area in Hunan province was investigated, using non derivatization gas chromatographic method. Seven tobacco samples were collected from three districts/counties, and the content of polybasic acids and higher fatty acids of them were detected. The results showed that the highest content of seven kinds of tobacco among the polybasic acids was propionic acid, followed by 2-Methylbutyric acid and 3-methylvaleric acid. Among the higher fatty acids, the highest content of seven kinds of tobacco was palmitic acid, followed by linoleic acid and oleic acid. Moreover, the content of these volatile and non volatile acid in upper leaves was found higher than in middle leaves. Using partial least squares regression analysis (PLSR) method, the correlation analyses of polybasic and higher fatty acids and their sensory quality of the tobacco leaf samples were also conducted. The results showed that the higher the content of polybasic acids was, the lower the sense of oral irritation was, and the more obvious of the smoke incense and the stronger of the smoke permeability as well. However, the higher fatty acids could only improve the suction of tobacco, and had a bad effect on other sensory indexes.