AbstractThe presence of alkene moieties in fatty acids of (phospho)lipids and cholesterol derivatives makes them highly susceptible to damage by nitrate radicals (NO3⋅), potentially formed through simultaneous exposure to the environmental air pollutants nitrogen dioxide (NO2⋅) and ozone (O3). Absolute rate coefficients derived from reactions with simplified model systems range from 4 to 8×109 M−1 s−1 in acetonitrile, ranking among the highest determined for NO3⋅ reactions with biomolecules in solution to date. Alkenes featuring an electron‐withdrawing carbonyl substituent also display notable reactivity with k values of (2.5±1.0)×108 M−1 s−1. Calculations suggest that these reactions are initiated by oxidative electron transfer (ET) involving the C=C bond, followed by recombination of the resulting alkene radical cation with nitrate anion (NO3−) to form the nitrate adduct radical as the kinetically controlled product. Conversely, saturated fatty acid derivatives and cholestanol react with NO3⋅ through hydrogen atom transfer (HAT) with rate coefficients of 106–107 M−1 s−1, indicating that biomolecules with a considerable number of non‐ or moderately activated sp3 C−H bonds are also highly susceptible to NO3⋅ attack. These findings underscore the potential health hazards associated with exposure to combined NO2⋅ and O3 gases.