Atmospheric concentrations of polychlorinated naphthalenes (PCNs) (108 samples in total) were measured at two rural/semirural sites in England and one remote site on the west coast of Ireland in the years 2001 and 2000, respectively. Detailed analysis of the factors affecting concentrations is performed. At Mace Head (MH) Ireland, concentrations of ΣPCNs ranged between 1.7 and 55 pg m-3 with a mean of 15 pg m-3 and were controlled primarily by advection. ΣPCNs concentrations at Hazelrigg (HR), northwest England, ranged between 31 and 310 pg m-3 with a mean of 110 pg m-3, and at Chilton (CH), southwest England, ranged between 31 and 180 pg m-3 with a mean of 85 pg m-3. Data from the HR site shows that PCN concentrations have not declined between the early 1990s and 2001, while PCB concentrations have declined. The ratio of the ΣPCNs/ΣPCBs was close to or greater than 1 at all sites. From air mass back trajectories, it is clear that local/regional sources influenced concentrations of PCNs at all sites, particularly at MH. At the two English sites during the summer, concentrations of PCNs were strongly influenced by temperature, indicating that air−surface exchange processes play an important role. Advection became more influential during winter, particularly at CH, where a different homologue profile was observed in some samples when air masses approached from the southwest and PCN concentrations increased. The average mixture profile of PCNs in air was similar to that observed in other studies and different from that in Halowax 1014.