Abstract: The concentration of organic acids and free fatty acids in 12 kinds of Chinese rice wine from different areas were determined by high performance liquid chromatography (HPLC) and gas chromatography (GC) . Nine kinds of organic acids and five kinds of free fatty acids were studied further through principal component analysis (PCA) . Results showed that the content of lactic acid, acetic acid and citric acid were the most, which accounted for more than 80% of the total organic acids. First four principal components could represent 85.276% sample information. And the principal components value reflected that origin, raw materials and technology of Chinese rice wine were significantly correlation with the content of organic acids in Chinese rice wine. It was also found that there was a wide variety of free fatty acids in 12 kinds of Chinese rice wine, and the difference in the total content of free fatty acids in Chinese rice wine was significant. The accumulative contribution rate of the first principal component and the second principal component reached 61.783% and 83.822% respectively, which could indicate the original information. The first principal component comprised C18∶0and C16∶0and the second component comprised C14∶0and C18∶1. These 4 kinds of compounds which affected the overall flavor of Chinese rice wine could be divided into three types :C18∶0and C16∶0, C14∶0, C18∶1.