A comparison of results obtainable by two different procedures available to carry out stereospecific analysis of natural triacylglycerols, as those of extra virgin olive oil, is reported. The characteristics of the two procedures, the first one chemical-enzymic-instrumental and the second chemical-instrumental, are considered, in order to carry out a selection of the most effective for a reliable evaluation of quality of natural oils, especially when a deepened analysis, at molecular level, is required to analyze natural matrixes. In fact, according to the considerations pertaining the biosynthetic pattern of natural triacylglycerols and relative enzyme equipment, consequent to a species-specific genetic printing, it's reasonable to think that only the evaluation of isomeric/enantiomeric triacylglicerolic molecular species and, particularly, of their relationships can be useful to assess the oil quality