Intestinal in vitro digestion of 1,3-diolein (DO), 1-monoolein (MO), DO:MO (1:1) rich oils, and triolein (TO), was performed to study the rate and extent of hydrolysis as well as their bioaccessibility in detail, with special emphasis on 1,3-DO and 1-MO forms, as potential bioactive lipids with additional technological functions such as self-emulsifying lipids. The importance of in vitro conditions on non-desirable acylmigration was also shown. The rate of in vitro intestinal lipolysis was in increasing order TO95%) of DO, MO and DO:MO were found within the micellar phase fraction during digestion, suggesting a high bioaccessibility. A positive correlation between the degree of lipolysis and the number of mixed micelles formed at the end of digestion was found. As summary, the obtained results would enhance the selection of glycerides to formulate ingredients with different purposes. Thus, in case a final high level of 1-MO would be desired to take advantage of the bioactivity of 1-MO, oils under the form of DO or DO:MO might be superior to MO. In case a high 1-MO level together with a low 2-MO level would be desired at the same time, mixtures of DO:MO or MO would be preferred. In case a higher self-emulsifying ability would be desired, the preferred forms would be MO and DO:MO. Finally, in case all the potential functionalities would be desired at the same time, namely the highest bioactivity, together with a high self-emulsifying ability, the mixture DO:MO might be suggested as an interesting product, with the additional economical advantage.