When plant sterols are oxidized at moderate temperatures (≤100 °C), products mainly derive from hydroperoxides, but at temperatures close to 200 °C, thermal reactions such as dehydration and condensation become important. Although sterols are often subjected to frying conditions, very little is known of their thermal reactions. In this study, stigmasterol was thermo‐oxidized at 180 °C, and the formation of dimers and polymers and the amounts of monomers were measured by high‐performance size‐exclusion chromatography. The products were further characterized by polarity using solid‐phase extraction fractionation. During heating, the amounts of monomers decreased at a steady rate, and those of dimers and polymers increased. After 3 h of heating, 21% of the material existed in higher‐molecular‐weight products. The amount of polar monomers increased especially during the first hour, demonstrating the formation of oxides and their further reactions, while that of mid‐polar monomers decreased constantly, indicating losses of stigmasterol. Polar dimers contributed to approximately 60% of the dimers, and polar polymers to approximately 78% of the polymers, which suggests that in most higher‐molecular‐weight products at least one of the sterol moieties was oxidized. This study showed that a significant proportion of thermo‐oxidation products are not polar monomeric oxides which are commonly analyzed as oxidation products.