Classification of brands and quality of food products is a very active area with the application of chemometric classification procedures. The content of inorganic elements such as Mg, K, Pb, Zn, Fe, Mn, Ca and Cu in 32 vinegar samples was determined by atomic absorption spectrophotometer. The similarity of Chencu and Baicu as well as different brands of vinegar samples of the same kind was calculated by vector similarity analysis. The characteristic discrimination of vinegar samples of four brands from Beijing, Jiangxi, Jiangsu and Shanxi was accomplished through cluster analysis and principal component analysis, and the classification of different kinds of vinegar samples (Chencu and Baicu) was performed as well. Vinegar samples were divided into two main groups by cluster analysis and principal component analysis. Each main group was discriminated according to different brands. The contents of inorganic elements in vinegar were good chemical descriptors for differentiation of their kinds and brands.