Maytenus ilicifolia or "Espinheira-Santa" is a renowned Brazilian medicinal plant usually used against intestinal and stomach ulcers. Other species with similar thorny leaves have raised great confusion in order to discern the authentic M. ilicifolia. Misidentifications can lead to product adulteration of authentic M. ilicifolia with other species, which can be found on the Brazilian market. The intake of misclassified herbal products potentially could be fatal, demanding faster reliable fingerprinting-based classification methods. In this study, the use of 1 H HR-MAS NMR metabolomics fingerprinting and principal component analysis (PCA) allowed an evaluation of the authenticity for both collected and commercial M. ilicifolia samples, from the content of the flavanol, (−)-epicatechin (2), by observing variations in metabolic patterns. Plant specimen types from cultivated and natural habitats were analyzed by considering seasonal and topological differences. The interand intraplant topological metabolic profiles were found to be affected by seasonal and/or ecological trends such as sunlight, shade, rain, and the presence of pathogens. Moreover, several commercial samples, labeled as M. ilicifolia, were evaluated, but most of these products were of an inadequate quality.T he use of medicinal plants is a foundation of folk medicine in several countries, including Brazil. Some plants offer therapeutic attributes due to the presence of various chemical compounds, and on proper use, they can treat several diseases. However, the intake of misclassified, false, or wrongly labeled unauthentic plants or their products may be fatal. Usually, false products can comprise foreign matter, toxic plant ingredients, or harmful chemical additives that can have adverse effects. 1−3 Brazil has several renowned medicinal plants from the Maytenus genus. This genus represents about 300 species, including Maytenus ilicifolia Mart. ex Reissek (Celastraceae) (synonyms: Celastrus pinifolius Larranãga; Maytenus angustior Briq.; Maytenus hassleri Briq.; Maytenus muelleri Schwacke; Maytenus off icinalis Mabb.; Maytenus pilcomayensis Briq.; and Maytenus aquifolium Mart.). This species is known popularly as "Espinheira-Santa", and it is distributed in different regions of Brazil. 4 According to the Brazilian Pharmacopeia, the leaves of this species have several marker constituents (e.g., flavonoids) and are largely consumed as an infusion (tea), as the raw material, or as extracts and capsules. 4,5 Also, M. ilicifolia and/or M. aquifolium have been cited in the "National List of Medicinal Plants of Interest to the Unified Health System (RENISUS)", and this list contains 71 medicinal plants of interest for therapeutic use by the Brazilian population. 6