Virgin olive oil and olive–pomace oil constitute high nutritional value edible oils due to the presence of oleic acid and a variety of bioactives. Among the latter, the group of pentacyclic triterpenes (PcTr) is the least studied. This review provides an insight into the biosynthesis of PcTr in the olive fruit, mainly of oleanane-type, and the factors influencing their transfer to the oil. Particular attention is given to the extraction methods along with the liquid and gas chromatography coupled to mass spectrometry protocols used for the discrimination and determination of PcTr. The in vivo bioactive properties of PcTr through the intake of these oils against cardiovascular diseases, liver dysfunction, obesity and diabetes are presented with a prospect of a future health claim authorization. Gaps in literature are pointed out to support this goal.