Vehicle emissions are an important source of nitrated aromatic compounds (NACs) in particulate size smaller 2.5 μm (PM_2.5), which adversely affect human health and biodiversity, especially in urban areas. In this study, filter-based PM_2.5 samples were collected during October 14–19, 2019, in a busy urban tunnel (approximately 35,000 vehicles per day) in south China to identify PM_2.5-bound NACs. Among them, 2,8-dinitrodibenzothiophene, 3-nitrodibenzofuran and 2-nitrodibenzothiophene were the most abundant nitrated polycyclic aromatic hydrocarbons (NPAHs), while 2-methyl-4-nitrophenol, 2,4-dinitrophenol, 3-methyl-4-nitrophenol and 4-nitrophenol were the most abundant nitrophenols (NPs). The observed mean fleet emission factors (EFs) of NPAHs and NPs were 2.2 ± 2.1 and 7.7 ± 4.1 μg km⁻¹, and were 2.9 ± 2.7 and 10.2 ± 5.4 μg km⁻¹ if excluding electric and liquefied petroleum gas vehicles, respectively. Regression analysis revealed that diesel vehicles (DVs) had NPAH-EFs (55.3 ± 5.3 μg km⁻¹) approximately 180 times higher than gasoline vehicles (GVs) (0.3 ± 0.2 μg km⁻¹), and NP-EFs (120.6 ± 25.8 μg km⁻¹) approximately 30 times higher than GVs (4.1 ± 0.2 μg km⁻¹), and thus 89% NPAH emissions and 56% NP emissions from the onroad fleets were contributed by DVs although DVs only accounted for 3.3% in the fleets. Methanol solution-based light absorption measurements demonstrated that the mean incremental light absorption for methanol-soluble brown carbon at 365 nm was 6.8 ± 2.2 Mm⁻¹, of which the 44 detected NACs only contributed about 1%. The mean EF of the 7 toxic NACs was approximately 3% that of the 16 priority PAHs; However, their benzo(a)pyrene toxic equivalence quotients (TEQ_BaP) could reach over 25% that of the PAHs. Moreover, 6-nitrochrysene mainly from DVs contributed 93% of the total TEQ_BaP of the NACs. This study demonstrated that enhancing DV emission control in urban areas could benefit the reduction of exposure to air toxins such as 6-nitrochrysene.