Daniellia oliveri is one of the most extensively utilized medicinal plants in Nigeria and some West African countries for the treatment of various ailments. In the present study, the GC-MS profiles and effect of ethanolic extracts of stem bark and leaves of Daniellia oliveri on lipid peroxidation, Na+/K+-ATPase activity and thiols status in H2O2 and Fe2+ (fenton reaction) assaulted cerebral and hepatic tissue homogenates was investigated. The stem bark and leaves were extracted with absolute ethanol for 72hrs and concentrated in a rotary evaporator. Wistar rats were euthanized and the brains and livers were removed, homogenized, centrifuged and the supernatants were used for lipid peroxidation, Na+/K+-ATPase activity, and thiol assays in the presence of prooxidants (1mM H2O2 or 10μM Fe2+ or H2O2 and Fe2+).The results revealed that ethanol extract of both the leaf and stem-bark inhibited lipid peroxidation induced by H2O2, Fe2+ and combination of H2O2 and Fe2+ and this was evident in the reduction of lipid peroxidation adducts formation in rat liver and brain homogenates with the stem-bark possessing more efficacy. Furthermore, the results of Na+/K+-ATPase and thiol assays revealed that H2O2 and Fe2+ inhibited the activity of cerebral Na+/K+-ATPase, while H2O2/Fe2+ caused a marked reduction in the levels of both protein and non-protein thiols in the tissues homogenates. However, the ethanolic extract of Daniellia oliveri extirpated this anomaly by increasing the activity of cerebral Na+/K+-ATPase as well as the thiol level in the rat hepatic and cerebral tissues. Finally, GC-MS analysis was carried out on the ethanolic extracts of the stem bark and leaves of Daniellia oliveri and results revealed the presence of 21 compounds including 1,2-Benzisothiazol-3-amine, 1H-Indole-2-carboxylic acid, 2-Ethylacridine, Ethyl 2-(2-chloroacetamido)-3,3,3-trifluoro-2-(3-fluoroanilino) propionate and trans-1-Butyl-2-methylcyclopropane in the stem bark and 10 compounds including Methylthio-acetonitrile, 2-Methyl-Z,Z-3,13-octadecadienol, Desulphosinigrin and 4H-1,2,4-triazole-3,5-diamine in the leaves, justifying the observed biological activities of Daniellia oliveri and the higher potency of the stem bark may be attributed to the presence of more bioactive constituents found in it. This study therefore justifies the medicinal usage of leaves and stem-bark of Daniellia oliveri and suggests its consideration in the treatment and management of degeneration diseases with etiology associated with oxidative stress.