Semipermeable membrane devices (SPMDs) were deployed at 19 sites in northwest England to test their efficacy as passive atmospheric samplers for polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs). SPMDs were found to be efficient samplers for vapor phase species in the atmosphere, with good reproducibility between samplers. Species which are partially or completely particle associated under ambient U.K. conditions were also sampled by the SPMDs but with poorer reproducibility. It is suggested that SPMDs could be used to indicate “hot-spots” of particulate associated species, however. Differences in absolute and relative concentrations of all PCDD/Fs and PAHs sequestered by the SPMDs were observed between sites. High amounts were sequestered in SPMDs at sites where previous active monitoring has indicated relatively high atmospheric concentrations, confirming the potential of SPMDs as a tool for semiquantitative spatial monitoring of atmospheric species. SPMDs also respond to differences in the mixture of compounds present in the atmosphere, thereby aiding source apportionment studies.