ABSTRACT Calophyllum brasiliense Cambess . is a native Brazilian tree rich in bioactive compounds, such as coumarins, xanthones, and chromanones. This study investigated the chemical composition of four morphotypes of the species using Fourier‐transform infrared spectroscopy (FTIR) and electrospray ionization mass spectrometry (ESI‐MS). FTIR revealed functional groups related to phenolic compounds and allowed the chemical distinction among the morphotypes. Hierarchical cluster analysis classified the samples into two distinct groups, while principal component analysis (PCA) indicated that the first component (PC1) explained 96% of the variation. Spectral regions between 3500–3100, 1050, and 870 cm ‒1 were crucial for differentiation. ESI‐MS identified compounds such as mammea, jacareubin, and inophyllum, highlighting chemical differences among the morphotypes. These results reinforce the potential of C. brasiliense as a source of phenolic compounds and emphasize the chemical variations among its morphotypes, which may help in exploring bioactive properties and future applications in pharmacology.