The oxidative stability and fatty acid composition of groundnut seed oil (GSO) exposed to microwaves were evaluated during heating at 170 °C. During heating, the oxidative indices such as free fatty acid, peroxide value, p-anisidine value, TOTOX, thiobarbituric acid value, specific extinctions, and color value were increased. The increments were found to be higher in unroasted seed oils compared to roasted ones indicating lower release of lipid oxidation products in roasted GSO. After 9 h heating, the relative content of polyunsaturated fatty acid (PUFA) decreased to 89.53% and that of saturated fatty acid (SFA) increased to 117.46% in unroasted sample. The relative content of PUFA decreased to 92.05% and that of SFA increased to 105.76% in 7.5 min roasted sample after 9 h of heating. However, the roasting process slowed down the oxidative deterioration of PUFA. With increased heating times, an appreciable loss was more apparent in the triacylglycerol species OLL and OOL in unroasted samples compared to roasted ones. In FTIR, the peak intensities in unroasted samples were markedly changed in comparison with roasted samples during heating. The roasting of groundnut seed prior to the oil extraction reduced the oxidative degradation of oil samples; thereby increasing heat stability.