It has been known that the polybrominated dibenzo- p-dioxins/furans (PBDD/Fs) share similar or even higher toxicity and bio-accumulativity with polychlorinated dibenzo- p-dioxins/furans (PCDD/Fs). In this study, the co-analysis method of PBDD/Fs and PCDD/Fs with isotope dilution HRGC-HRMS was built based on the U.S. EPA Method 1613 and TO-9A. The samples were extracted and cleaned through acid silica gel bed, multi-layer silica gel column, and Florisil column, respectively. Eight 2,3,7,8-PBDD/Fs congeners and 17 congeners of 2,3,7,8-PCDD/Fs were quantified. The HRGC-HRMS conditions for PBDD/Fs were: EI + and SIM model with resolution ≥ 10000, electron emission energy of 50 eV, and filament current of 0.75 mA; DB-5 MS fused silica capillary column (30 m × 0.25 mm i.d., 0.1 μm) was used and the temperatures for injection, ion source, and transfer line were 250 °C, 250 °C, and 305 °C, respectively. The carrier gas was helium (1.0 ml min −1). The results showed that the relative standard deviations (RSDs) of parallel blank samples were ≤ 10.3% and the recoveries of PBDD/Fs and PCDD/Fs were in the range of 73%–112%. The average quantified values of the standard reference sample were in accordance with the certified values and the RSDs were ≤ 12.0%. The method detection limits were 0.25–1.5 pg μl −1 for PBDD/Fs and 1.5–5 pg μl −1 for PCDD/Fs. The concentrations of PBDD/Fs and PCDD/Fs were 1.01–2.43 pg per m 3 and 6.19–10.8 pg per m 3 for particulate samples, and 0.036–0.801 pg per m 3 and 1.37–12.1 pg per m 3 for gaseous samples of certain area, respectively. Compared with other areas in the world, the atmospheric dioxins pollution of the sampling area was at high level.