A normal diet contains large quantities of oxidized fatty acids, glycerolipids, cholesterol, and their cytotoxic degradation products because many foods in the diet are fried, heated, or otherwise processed and consumed often after long periods of storage. There is also evidence that the acid medium of the stomach promotes lipid peroxidation and that the gastrointestinal tract is a major site of antioxidant action, as demonstrated by various colorimetric methods. The identity and yields of specific products of lipid transformation have seldom been determined. The present study describes the molecular species profiles of all major gastrointestinal lipids formed during digestion of autoxidized rapeseed oil in an artificial digestion model in the presence of L-ascorbic acid, 6-palmitoyl-O-L-ascorbic acid, 3,5-di-tert-butyl-4-hydroxytoluene (BHT), DL-α-tocopherol, and DL-α-tocopheryl acetate. Differences in oxidized lipid profiles were detected in the samples digested in the presence of different antioxidants, but none of them could prevent the formation of oxidized lipids or promote their degradation in a gastric digestion model. The lack of effect is attributed to the inappropriate nature of the gastrointestinal medium for the antioxidant activity of these vitamins and BHT. A fast ultrahigh performance liquid chromatographic-electrospray ionization-mass spectrometric method was developed for the analysis of lipolysis products, including epoxy, hydroperoxy, and hydroxy fatty acids, and acylglycerols, utilizing lithium as ionization enhancer.