A nation-wide passive air sampling campaign recorded concentrations of persistent organic pollutants in Australia's atmosphere in 2012. XAD-based passive air samplers were deployed for one year at 15 sampling sites located in remote/background, agricultural and semi-urban and urban areas across the continent. Concentrations of 47 polychlorinated biphenyls ranged from 0.73 to 72 pg m(-3) (median of 8.9 pg m(-3)) and were consistently higher at urban sites. The toxic equivalent concentration for the sum of 12 dioxin-like PCBs was low, ranging from below detection limits to 0.24 fg m(-3) (median of 0.0086 fg m(-3)). Overall, the levels of polychlorinated biphenyls in Australia were among the lowest reported globally to date. Among the organochlorine pesticides, hexachlorobenzene had the highest (median of 41 pg m(-3)) and most uniform concentration (with a ratio between highest and lowest value ∼5). Bushfires may be responsible for atmospheric hexachlorobenzene levels in Australia that exceeded Southern Hemispheric baseline levels by a factor of ∼4. Organochlorine pesticide concentrations generally increased from remote/background and agricultural sites to urban sites, except for high concentrations of α-endosulfan and DDTs at specific agricultural sites. Concentrations of heptachlor (0.47-210 pg m(-3)), dieldrin (ND-160 pg m(-3)) and trans- and cis-chlordanes (0.83-180 pg m(-3), sum of) in Australian air were among the highest reported globally to date, whereas those of DDT and its metabolites (ND-160 pg m(-3), sum of), α-, β-, γ- and δ-hexachlorocyclohexane (ND-6.7 pg m(-3), sum of) and α-endosulfan (ND-27 pg m(-3)) were among the lowest.