Oils from cv. Arbequina were industrially extracted together with olive leaves of cv. Arbequina or Santulhana (1%, w/w), and their olfactory and volatile profiles were compared to those extracted without leaves addition (control). The leaves incorporation resulted in green fruity oils with fresh herbs and cabbage olfactory notes, while control oils showed a ripe fruity sensation with banana, apple, and dry hay grass notes. In all oils, total volatile contents varied from 57.5 to 65.5 mg/kg (internal standard equivalents), being aldehydes followed by esters, hydrocarbons, and alcohols the most abundant classes. No differences in the number of volatiles were observed. The incorporation of cv. Arbequina or Santulhana leaves significantly reduced the total content of alcohols and esters (minus 37–56% and 10–13%, respectively). Contrary, cv. Arbequina leaves did not influence the total content of aldehydes or hydrocarbons, while cv. Santulhana leaves promoted a significant increase (plus 49 and 10%, respectively). Thus, a leaf-cultivar dependency was observed, tentatively attributed to enzymatic differences related to the lipoxygenase pathway. Olfactory or volatile profiles allowed the successful unsupervised differentiation of the three types of studied cv. Arbequina oils. Finally, a lab-made electronic nose was applied to allow the nondestructive discrimination of cv. Arbequina oils extracted with or without the incorporation of olive leaves (100% and 99 ± 5% of correct classifications for leave-one-out and repeated K-fold cross-validation variants), being a practical tool for ensuring the label correctness if future commercialization is envisaged. Moreover, this finding also strengthened that olive oils extracted with or without olive leaves incorporation possessed quite different olfactory patterns, which also depended on the cultivar of the olive leaves.