The effect of γ-tocopherol in proportions between 0.02 and 2% by weight on the accelerated storage process of refined soybean oil is studied by 1H NMR, and compared with that of α-tocopherol. Whereas the lowest γ-tocopherol enrichment level does not affect oil evolution, at higher concentrations both γ- and α-tocopherols initially accelerate acyl groups degradation and hydroperoxides generation, more as higher is the tocopherol concentration, this effect being less marked for γ-tocopherol. However, after this initial stage, the rates of acyl groups degradation and hydroperoxides formation decrease with tocopherol concentration. Furthermore, in the case of γ-tocopherol, the higher the enrichment degree, the later hydroperoxides decomposition occurs, so that, unlike α-tocopherol, γ-tocopherol delays the generation of most secondary oxidation products (aldehydes, (E,E)-keto-dienes, epoxy-keto-enes, (E)-epoxystearates and alcohols) with the exception of some epoxides. Similarly to α-tocopherol, γ-tocopherol modifies the oil oxidation pathway at the highest addition level, promoting the formation of compounds with (Z,E)-isomerism, although less noticeably than α-tocopherol.