Phytochemical analysis of the root bark extract of Maytenus cuzcoina (Celastraceae) led to the isolation and characterization of sixteen triterpenoids with a 6/6/6/6/6 pentacyclic system, including the new 22α-hydroxy-29-methoxy-3β-tetradecanoate-olean-12-ene, and 3β,24β-epoxy-29-methoxy-2α,3α,6α-trihydroxy- D:A-friedelane that is reported for the first time as a natural product. This is the first instance of the isolation of a tetradecanoate triterpene ester from a Celastraceae species. The structures were elucidated on the basis of spectrometric and spectroscopic methods, including 1D and 2D NMR techniques.