Little is known about the structure and molecular arrangement of α- and β-amyrin, a class of triterpenoids found within the cuticle of higher plants. Blends of both amyrin isomers with different ratios have been studied taking into consideration a combined methodology of density functional theory (DFT) calculations with experimental data from scanning electron microscopy, differential scanning calorimetry and Raman vibrational spectroscopy. Results indicate that trigonal trimeric aggregations of isomer mixtures are more stable, especially in the 1 : 2 ( α : β ) ratio. A combination of Raman spectroscopy and DFT calculations has allowed to develop an equation to determine the amount of β-amyrin in a mixed sample.