An efficient and reliable analytical method has been used for determination of polybrominated diphenyl ethers (PBDEs) in atmospheric total suspended particles collected from the six state controlling air sampling sites and two self-selection sampling sites in Kunming, China. The results showed that the overall average concentrations of TSP collected from Kunming were in the range of 44.36 μg/m3 to 82.22 μg/m3. This pattern was lower than the average concentrations of Guiyu, Guangzhou and similar to Hong Kong. In TSP, the penta-BDEs and octa-BDEs were the dominant PBDEs and the PBDEs concentration ranged from 12.39 pg/m3 to 71.51 pg/m3, with a mean value of 46.82 pg/m3. This level was below the city of Guiyu, Örebro in Sweden and similar to Hong Kong, Guangzhou. The average concentrations of PBDEs had the trend of descent from the urban center to the outskirts of Kunming.