Olive oil is an important component of Mediterranean diet widely, consumed thanks to its numerous health-healing properties. Its quality is dependent upon a set of factors (genotypic, environmental, agronomic practices, ripening, etc). These are well documented, but little is known about the impact of extraction technology on ‘Moroccan Picholine’ olive oil quality. In this paper, physicochemical traits of olive oil (cv ‘Moroccan Picholine’) were investigated according to extraction technology namely super pressure (SP), 2-phase (2P), and 3-phase (3P) systems as well as traditionally extracted oil (Alwana Oil, AO). The obtained results revealed significant differences (p < 0.05) in terms of the studied physicochemical traits. The investigated oil samples were classified as extra-virgin olive oil. Oil samples from super pressure and AO marked by high records of peroxide value, acidity, K270, fatty acids and trans fatty acids likely due to partial oxidation during extraction. AO was marked by high MUFA, stigmasterol, brassicosterol, 2P displayed high SFA and β-sitosterol, and 3P had high PUFA, SFA, ∆7-avenasterol, and ∆7-stigmasterol. These results were confirmed by principal component analysis, cluster analysis and artificial neural networks. In conclusion, continuous systems (2- and 3-phase) produced olive oil of better quality as compared to super-pressure and traditionally extracted oil.