Background: Pentacyclic triterpenes are plant secondary metabolites that have many applications for health of the people. Methods: In this work, we determine by a HPLC-UV/Vis and HPLC-MS what pentacyclic triterpenes are found in stem and root of cv. Picual olive tree, a variety typically grown in the area of Jaén (Spain). Moreover, the concentration of these compounds along fruit ripening also has been determined in both organs. Results: Maslinic acid (MA), oleanolic acid (OA), erythrodiol (EO), and uvaol (UO) have been found in stem. OA is the compound that shown the highest concentration in this organ. MA, betulinic acid (BA), OA and ursolic acid have been found in root. In general, BA has the highest concentration in this organ. BA had not been detected in other olive tree organs. Conclusion: The evolution showed by the concentrations of these compounds during ripening suggests the existence of two different phases: the first related with the increment in weight of fruit and the second related with the ripening following. The evolution found in stem is different to the found in root and we believe that are related with the functions of these compounds in each organ.