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Gamma-oryzanol, a phytosteryl ferulate mixture extracted from rice bran oil, has a wide spectrum of biological activities; in particular, it has antioxidant properties and is often used in cosmetic formulations as a sunscreen. The first objective of the present investigation was to elucidate the molecular mechanism(s) of the antioxidant activity of gamma-oryzanol by utilising different in vitro model systems, such as scavenging of stable DPPH• radical, OH• and O2•− radicals scavenging, and azocompound AMVN-initiated lipid peroxidation. The effect of gamma-oryzanol on the oxidative stability of vegetable oils of pharmaceutical and cosmetic interest was then evaluated in a oxidation accelerate test and compared with the effect of the well-known antioxidants BHA and BHT. Our results demonstrate that gamma-oryzanol is an organic radical scavenger able to prevent AMVN-triggered lipoperoxidation. Moreover, when added to oils at concentrations ranging between 2.5 and 10 mmol/kg, gamma-oryzanol shows a dose-dependent increase of the induction times; in particular, it improved the oxidative stability of oils very prone to lipoperoxidation because of their high content of polyunsaturated fatty acids. On the ground of our results, we can conclude that gamma-oryzanol may have a potential application for the stabilization of lipidic raw materials.