In this study, we investigated the antioxidative functions of carotenes (CARs) against the peroxidation of lipids initiated by nitrogen dioxide using density functional theory. The hydrogen-atom transfer (HAT), radical adduct formation (RAF), and electron transfer (ET) mechanisms were investigated. We chose β-carotene (β-CAR) and lycopene (LYC) and compared their NO2(•) initiations and peroxidations with those of linoleic acid (LAH), the model of the lipid. We found that for CARs ET is more likely to occur in the most polar (water) environment than are HAT and RAF. In less polar environments, CARs react more readily with NO2(•) via HAT and RAF than does the lipid model, LAH. Comparatively, reaction barriers for the RAF between CARs and NO2(•) are smaller than those for the HAT. The additions of O2 to the radical intermediates O2N-CAR(•) and CAR(-H)(•) involve sizable barriers and are endergonic. Other than HAT of LAH, we revealed that lipid peroxidation is likely to be initiated by -NO2 addition and the subsequent barrierless addition of O2. Finally, LYC is a more effective antioxidative agent against NO2(•)-initiated lipid peroxidation than is β-CAR.