An analytical method for the quantification of Polychlorinated biphenyls (PCBs) concentrations in XAD-2 passive air samplers (PAS) and tree barks collected close to the Rhine River between France and Germany was developed. This method used Accelerated Solvent Extraction (ASE) followed by a purification step by flash chromatography using a 4gr cartridge (3g of silica gel and 1g of 44% acidified silica) and analysis by GC–ECD with dual columns.Quantification (QL) and detection (DL) limits varied 0.5 from and 5.7ngPAS −1 and from 0.5 and 3.0ngPAS −1 respectively. For tree barks, quantification and detection limits were calculated for each congener on washed tree bark sample with a signal to noise ratio of 3:1 and 10:1 (corresponding to a LQ in the range of 1–4ng per bark sample by congeners).Uncertainties on each congener concentration were calculated to be in the range of 3–20% XAD-2 passive samplers were field calibrated by using Hi-vol. Samplers. Sampling rates of 4.2, 11.5, 1.6, and 7.9m 3 PAS −1 d −1 for tri-, tetra-, penta- hexa-PCBs, respectively were obtained and are comparable to those already obtained with PUF-PAS for gas phase only (gas/particle distribution was 90/10).Method was applied to real atmospheric samples collected by XAD-2 passive samplers and tree barks in the east of France.