Extra virgin olive oil (EVOO) production in Brazil is recent and growing, but only a few studies have been published on the topic, specially involving commercial EVOO samples. A preliminary discrimination of Brazilian EVOOs according to olives’ cultivar and region of production was pursued. A principal components analysis (PCA) and a partial least squares discriminant analysis (PLS-DA) were performed based on the results of a recent published work by our research group on the evaluation of the quality parameters, the metabolic profile, and other typical features of ten commercial EVOOs from Brazil. One of the oleuropein aglycone isomers, linoleic acid, α-tocopherol and free sterols were pointed out as the most influential variables within the models. PLS-DA also revealed the region of production as a significant factor to samples’ clustering. The present work provides a preview of Brazilian EVOOs typicity and shows the urge for more investigations with higher number of commercial samples, from different olives´ cultivars and production regions. The comprehensive definition of their chemical profile’s identity could provide Brazilian oils with a significant added value.