Abstract Detailed polychlorinated biphenyls (PCBs) congener patterns were determined in the flue gas from a medical waste incinerator (MWI) using high-resolution gas chromatograph coupled to high-resolution mass spectrometer (HRGC/HRMS). The total PCBs concentration of all homologues (mono- to deca-chlorinated homologues) in the flue gas ranged from 138.01 to 855.35 ng/Nm 3 and the WHO-TEQ value varied from 0.046 to 0.549 ng/Nm 3 under the different operating conditions. PCB-77 concentration was the highest among dioxin-like PCBs and PCB-126 contributed mostly to the WHO-TEQ. The ratios of dioxin-like PCBs in the total PCB concentrations in the flue gas varied between 11.7% and 26.0% (the average value is 18.7%). Three inhibitors, sulfur, urea, and ammonium sulfate were tested to investigate the capacity for preventing PCBs formation. The decomposition efficiency for total PCBs and PCBs TEQ ranged from 38% to 84% and 69% to 92% respectively. It was shown that urea mixed with ammonium sulfate and more activated carbon was proved to be the most effective inhibitor for PCBs formation. The removal efficiencies (REs) of the total PCBs concentration and PCBs TEQ by the bag filter under two conditions were 69% and 85%, and 86% and 94% respectively.