to their quality level (i.e., extra virgin, virgin or lampante olive oils) or autochthonous olive cultivar (i.e., cv Chétoui and cv Shali) was evaluated for the first time. Linear discrimination analysis coupled with the simulated annealing variable selection algorithm showed that the signal profiles of olive oils' hydroethanolic extracts allowed olive oils discrimination according to physicochemical quality level (classification model based on 25 signals enabling 84 ± 9% correct classifications for repeated K-fold cross-validation), and olive cultivar (classification model based on 20 signals with an average sensitivity of 94 ± 6% for repeated K-fold cross-validation), regardless of the geographical origin and olive variety or the olive quality, respectively. The results confirmed, for the first time, the potential discrimination of the electronic tongue, attributed to the observed quantitative response (sensitivities ranging from −66.6 to +57.7 mV/decade) of the E-tongue multi-sensors towards standard solutions of polar compounds (aldehydes, esters and alcohols) usually found in olive oils and that are related to their sensory positive attributes like green and fruity.