Work was carried out on the characterization of monovarietal virgin olive oils (VOO) from Tunisia and Sicily (Italy). The two main Tunisian VOO (cvv. Chétoui of the North and cv. Chemlali grown in the Center and some regions of the South) and three principal Sicilian VOO (cvv. Nocellara del Belice, Biancolilla and Cerasuola) were studied. Moreover, the Chétoui oils were tested in a rain-fed control and an irrigation regime. All olive samples were picked at three different stages of ripeness. Analyses of major components (fatty acids and triacylglycerols) and minor ones (squalene, tocopherols and phenolic compounds) were carried out. Chétoui oils had a higher level of phenolic compounds followed by Chemlali. Generally, in the Sicilian oils these natural antioxidant contents were lower. These preliminary results indicate that it was possible to classify the Tunisian and Sicilian oils tested in their original growing area based on their chemical composition.