Centella asiatica (L.) Urban is an important herbaceous medicinal plant with a worldwide distribution. The herb possesses a medicinal value and is used extensively in traditional systems of medicine. The medicinal properties of the herb are attributed to the presence of characteristic triterpenoids and their saponins in the leaves. The major triterpenoids are asiaticoside, madecassoside and their aglycones asiatic acid and madecassic acid, respectively, among others. The present study reports a remarkable qualitative and quantitative variability in secondary metabolites in different accessions of C. asiatica L. as determined by high-performance liquid chromatography (HPLC) analysis. The accessions analyzed in this study can be considered as the core set of discrete chemotypes of C. asiatica. Considerable and contrasting biochemical variations were observed in the terpenoid profiles of the chemotypes. From the basic and applied phytochemical utility, this chemotypic variability in the total content of triterpenoids is important and interesting.