Abstract The application of dynamic hollow fiber liquid-phase microextraction (dynamic HF-LPME) and gas chromatography–mass spectrometry (GC–MS) for the determination of trace amounts of polychlorinated biphenyls (PCBs) in water was investigated. The experimental parameters were optimized. Under the optimum conditions, the concentration enrichment factors for PCBs were from 718-fold to 840-fold. The calibration curves were linear over a range of 0.05–90 μg/L, with a correlation coefficient ( r 2) of 0.9957–0.9979. The relative standard deviation (RSD) ranged from 3.4% to 5.8% for intra-day variation and from 4.1% to 7.3% for inter-day variation. The limits of detection (LODs, S/N = 3:1) were in the range of 13–41 ng/L. The recoveries for spiked water samples ranged from 85.9% to 92.0%.