The kinetics and nitroarene product yields of the gas-phase reactions of naphthalene-d8, fluoranthene-d10, and pyrene with OH radicals in the presence of NOx and in N2O5NO3NO2air mixtures have been investigated at 296 ± 2 K and atmospheric pressure of air. Using a relative rate method, naphthalene-d8 was shown to react in N2O5NO3NO2air mixtures a factor of 1.22 ± 0.10 times faster than did naphthalene, with the 1- and 2-nitronaphthalene-d7 product yields being similar to those of 1- and 2-nitronaphthalene from naphthalene. From the measured PAH concentrations and the nitroarene product yields, formation yields of 2-, 7-, and 8-nitrofluoranthene-d9 and 2- and 4-nitropyrene of 0.03, 0.01, 0.003, 0.005, and 0.0006, respectively, were determined from the OH radical-initiated reactions. Effective rate constants for the reactions of fluoranthene-d10 and pyrene with N2O5 in N2O5;NO3NO2air mixtures of ca. 1.8 × 10−17 cm3 molecule−1 s−1 and ca. 5.6 × 10−17 cm3 molecule−1 s−1, respectively, were derived. Formation yields of 2-nitrofluoranthene-d9 and 4-nitropyrene of ca. 0.24 and ca. 0.0006, respectively, were estimated for these reaction systems. 2-Nitropyrene was also observed to be formed in these N2O5NO3NO2 reactions, but was found to be a function of the NO2 concentration and, therefore, would be a negligible product under ambient NO2 concentrations. These product and kinetic data are consistent with ambient air measurements of the nitroarene concentrations.