Mineral elemental concentrations of 50 Chinese medicinal herbs in acid digests were determined by flame atomic absorption spectroscopy. The data were subjected to chemometric assessment to understand the association between the elements and to classify the herbal samples. Chemometric techniques, such as principal component analysis (PCA) and hierarchical cluster analysis (HCA) were used as classification techniques. PCA generated two principal components that explained 62% of the total variance in the data. HCA disclosed two significant groups of samples based on their elemental concentrations.