The trace-level environmental determination of polychlorinated biphenyls (PCBs) and 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) requires the use of delicate fractionation and analytical techniques such as high-resolution gas chromatography coupled with high-resolution mass spectrometry. The analytical requirements are even higher if atmospheric physicochemical processes of these persistent organic compounds (POPs) are to be studied in remote areas, where concentrations are very low. The optimization of a fractionation method, and of the high-resolution gas chromatography/ion trap tandem mass spectrometry system instrumental parameters enabled us to establish the optimum conditions for the determination of atmospheric PCBs and PCDD/Fs at the low pg or even fg m-3 level. By using this analytical procedure, we accomplished the reliable determination of ca. 54 PCBs and 17 PCDD/Fs individual congeners, of different chlorination level, in the gas and particulate phase of atmospheric aerosol samples collected from the Eastern Mediterranean basin. Furthermore, we were also able to study the atmospheric physicochemical and loss processes of PCBs, such as gas-particle partitioning, wet and dry deposition, and PCBs reaction with hydroxyl radicals.