This study set out to identify possible PCDD/F emission sources for different atmospheric environments in a highly industrialized city located in southern Taiwan. We collected stack flue gas samples from five main stationary emission sources of the municipal solid waste incinerators (MSWIs), medical waste incinerators (MWIs), electric arc furnaces (EAFs), secondary aluminum smelters (ALSs), and sinter plants to assess the characteristics of their PCDD/F emissions. For mobile sources, congener profiles reported in U.S. EPA's database for unleaded gas-fueled vehicles (UGFV) and diesel-fueled vehicles (DFV) were directly adopted owing to lack of local data. The congener profiles of the 2,3,7,8-substituted PCDD/Fs were selected as the signatures of these PCDD/F emission sources. We conducted PCDD/F samplings on atmospheric environments of four categories, including background, residential area, traffic area, and industrial area. Through PCA and cluster analyses, we found that traffic areas were most influenced by PCDD/F emissions from UGFV and DFV, while those of industrial areas were mainly influenced by metallurgical facilities and MWIs. The above results were further examined by using the methodology of the indicatory PCDD/Fs. We confirmed that traffic areas were contributed by traffic sources, but industrial areas were simply affected by metallurgical facilities rather than MWIs. In conclusion, besides the use of PCA and cluster analyses, the methodology of the indicatory PCDD/Fs should be conducted for further validation in order to prevent misjudgment.