The emission and distribution of polychlorinated debenzo-p-dioxins/dibenzofurans (PCDD/Fs) was investigated in two municipal solid waste incinerators (MSWIs) and one coal-fired power plant (PP) in southern Taiwan. Samples were collected from stack flue gases (SFG), bottom residues (BR), super heater (SH), economizer (EC), semi-dry absorber (SDA), bag filter (BF), and fly ash pit (FAP) in MSWIs. Stack flue gases, bottom residues and electrostatic dust collectors (ESD) in PP were also collected. In order to compare the difference between the results of MSWIs and PP, samples from SFG, BS, and FAP in a PP were also determined. Seventeen congeners of PCDD/Fs were analyzed by utilizing a high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS). Distributions of total PCDD/F-I-TEQ in each unit of MSWI-A and MSWI-B were SFG (0.3%, 0.07%), BR (3.9%, 0.62%), SH (0.17%, 0.24%), EC (4.2%, 0.05%), SDA (1.29%, 7.06%), and BF (90.14%, 91.97%), respectively. However, those in SFG, BS, and FAP of PP were 99.58%, 0.17%, and 0.25%, respectively. The above results indicated 99.5% PCDD/Fs were trapped in the fly ash of MWSI. On the other hand, 99.7% PCDD/Fs was emitted to the atmosphere from PP. The results of this study provide useful information for controlling PCDD/Fs in MSWIs and PP.