Extra-virgin olive oil (EVOO) from Mediterranean were analyzed by Ultraviolet–Visible (UV–Vis) spectroscopy and Independent Component Analysis (ICA). The use of ICA resolution provided information over dienes (primary oxidation compound), polyphenolic compounds, tocopherol, carotenoids and chlorophylls when EVOO was evaluated by UV–Vis spectroscopy. Based on these data, ICA could be used to determine the contribution of chemical compounds to the composition of EVOO produced in different regions from Mediterranean. The results suggest that the combination of UV–Vis measurements and ICA makes possible the EVOO evaluation, and can contribute to suggesting that a foodstuff comes from an alleged origin. The proposed methodology is a low cost, fast and sample preparation free methodology to highlights the EVOO characteristics produced in the Mediterranean region.