Particulate matter-bound polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) were first systematically studied in downtown (XT), suburban (GL) and rural (DA) sites in winter and summer in Hanoi, Vietnam, from 2019 to 2022. The mean concentrations of PAHs and NPAHs ranged from 0.76 ng m−3 to 50.2 ng m−3 and 6.07 pg m−3 to 1.95 ng m−3, respectively. The concentrations of PAHs and NPAHs in winter were higher than in summer, except for NPAHs in XT. We found the benzo[a]pyrene (BaP)/benzo[ghi]perylene (BgPe) ratio could effectively identify biomass burning in this study, in which a higher [BaP]/[BgPe] value indicates a greater effect of biomass burning on PAHs and NPAHs. The results indicated that atmospheric PAHs and NPAHs were mainly affected by motor vehicles (especially the unique motorcycles in Southeast Asia) in the summer in Hanoi. In winter, all sites were affected by the burning of rice straw to varying degrees, especially DA. The incremental lifetime cancer risk (ILCR) in Hanoi was first determined through ingestion, inhalation and dermal absorption. The results showed that residents in Hanoi faced high health risks, while females experienced higher health risks than males. The ingestion and dermal pathways indicated higher exposure risks than the usually considered inhalation pathway.