BACKGROUND Agaves are mainly used to produce alcoholic beverages such as tequila, mezcal and bacanora. However, the leaves constitute more than 50% of the plant and are not used in the production process, so they are considered waste. This plant material can be used as a source of bioactive compounds such as terpenes, flavonoids and saponins. Therefore, the objective of this study was to characterize the aglycone type of saponins and to quantify three steroidal sapogenins in leaves of five Agave species collected in different regions of Guerrero and Oaxaca, Mexico. RESULTS Analysis by gas chromatography–flame ionization detection of the hydrolyzed methanolic extracts showed that diosgenin and tigogenin were the most abundant sapogenins identified in the five Agave species. Differences in the content of these sapogenins were found in the same species collected in different localities. The leaves of Agave americana var. oaxacensis L. (Oaxaca) had the highest diosgenin‐derived saponin content, while the leaves of A. angustifolia Haw. (Guerrero) had the highest tigogenin‐derived saponin content. Only in A. cupreata was sarsasapogenin identified, all three sapogenins occurring in the leaves of this species. For the first time, information is provided on the aglycones of the saponins produced in A. potatorum Zucc. and A. karwinskii Zucc. CONCLUSION This study made it possible to compare the content of diosgenin and tigogenin‐derived saponins in leaves of Agave species from Guerrero and Oaxaca. This information will be useful for better utilization of this plant material and add value to the process of mezcal elaboration. © 2022 Society of Chemical Industry.