Magnetic solid phase extraction(MSPE) based on Fe3O4-grafted graphene oxide (Fe₃O₄@GO) was combined with thermal desorption-gas chromatography-tandem mass spectrom-etry(TD-GC-MS/MS) to develop an organic solvent free quantitative analysis method for the determination of 7 kinds of indicative polychlorinated biphenyls(PCBs) in water. The factors affecting the extraction efficiency, induding amount of Fe₃O₄@GO, extraction time and pH value of water sample, were investigated. Under the control of the optimized conditions, an excellent linearity was observed in the range of 2~100 ng/L for the 7 kinds of PCBs, with the correlation coefficients(r)＞0.98. The detection limits (S/N=3) and the quantitation limits (S/N=10) were 0.18~0.40 ng/L and 0.57~1.32 ng/L, respectively. The mean recoveries at 2 spiked levels ranged from 85.9% to 106.2% with relative standard deviations(RSD) of 4.0%~13.1%. The proposed method could be used in the monitoring of trace PCBs contaminants in water sample.