Extra virgin olive oil (EVOO) chemical composition is characterized by high content of monounsaturated fatty acids and minor compounds including phenols, sterols, tocopherols, squalene and volatile compounds. These components are related to EVOO quality in terms of healthy properties, shelf life alteration due to susceptibility to oxidative degeneration and sensory properties. In this work, the variability of 66 different chemical compounds, oxidative stability and sensory attributes of EVOO was analyzed in order to study the relationships among them and the effect of cultivar, growing location and their interaction on their expression. Partial least squares (PLS) regression models allowed accurate prediction for EVOO stability on the basis of the chemical composition of the oils, with marked positive influence of oleic acid and 3,4-DHPEA-EA phenol content on stability values, while poor prediction results were obtained for sensory attributes. Cultivar and location showed limited effect on the sensory properties of EVOO, even though the same factors provide significant effect for the rest of chemical compounds and stability. These results should be taken into account in breeding programs aimed to obtain new cultivars with improved EVOO characteristics and to determine the best cultivar to be planted in each environment.