The role of lipase to catalyze hydrolysis and transesterification of triacylglycerols (TAGs) was evaluated in model systems as well as in virgin olive oil. Tandem mass spectrometry was applied in the identification of modified TAGs, ionized by electrospray, formed during the incubation of selected TAGs with mono and di carboxylic acids. The oligomerization of TAGs was observed in authentic olive oil samples and verified in model systems under catalysis exerted by lipase, whose presence in olive oil was already documented. The hydrolytic pathways taken under enzymatic treatment is balanced by the formation of TAG oligomers that should not alter the nutritional value of the aliment. Copyright © 2012 John Wiley & Sons, Ltd.