Air samples were collected at different sites in and around two wastewater treatment plants (WWTPs) located in central Italy to determine the concentrations, compositional profiles and contribution to ambient levels of eight polybrominated diphenyl ethers (PBDEs). The investigated WWTPs were selected as they treat industrial wastewater produced by local textile industries along with municipal wastewater. PBDE concentrations within the WWTPs were higher than those measured at reference sites located 4 and 5 km away with BDE-209 dominating the BDE congener composition in all air samples in 2008. Ambient PBDE concentrations measured in and around the WWTPs and estimates of emissions from aeration tanks suggest that WWTPs are sources of PBDEs to ambient air. Principal component analysis and Pearson correlations confirmed this result. The effect of distance from the plant and wind direction on atmospheric concentrations was also investigated. Although the primary fate of PBDEs in WWTPs will be partitioning to sewage sludge, this study suggests that plants can provide a measurable source of these compounds to local ambient air.