This study presents concurrently sampled ambient air data for a range of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated naphthalenes (PCNs) at the continental scale. This was achieved with a passive air sampling system, by deploying polyurethane foam disks, which were prepared in one laboratory, sealed to prevent contamination, sent out by courier to volunteers participating in different countries, exposed for six weeks, collected, resealed, and returned to the laboratory for analysis. The study area was Europe, a region with a history of extensive persistent organic pollutants usage and emission, and with marked national differences in population density, the degree of urbanization and industrial and agricultural development. Samplers were deployed at remote, rural, and urban locations in 22 countries. Calculated air concentrations were broadly in line with those obtained by conventional active air sampling techniques, for both compound classes and for compounds existing predominantly in the gas and particle phases. The geographical compound distribution reflected suspected regional emission patterns and highlighted localized source areas. Both PAH and PCN levels varied by more than two orders of magnitude. The implications for sources are discussed.