Abstract: A method for the determination 7 polychlorinated biphenyls (PCB 28, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 and PCB 180) in soil samples was developed. Solid samples were pretreated with accelerated solvent extraction and purified with sulfonation combining with Florisil solid phase extraction (SPE) and the concentrations of PCBs in soil samples were quantified by gas chromatograph with electron capture detector (GC-ECD) and further confirmed by gas chromatography-mass spectrometry (GC-MS). The detection limits of method (L_MD) for PCBs were 0.15~0.50 μg/kg and the recoveries were 80.06%~100.28% with the precisions of 1.01%~6.28% RSD. The method has been applied to the determination of PCBs in complex matrix soil sample with characters of high efficiency, good purification effect, high precision and accuracy and environment friendly.