We examined the characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and chlorobenzenes (CBzs) in the flue gas and fly ash of a municipal solid-waste incinerator in four locations: the outlet of the furnace, the outlet of the high-temperature superheater, the inlet of the semi-dry scrubber and the stack after air pollution control device (APCD) processing. Both PCDD/Fs and CBzs were mostly formed at low temperatures. The dominant PCDD/Fs generated in the gaseous phase were 23478-PeCDF and TCDF, and 124-TrCBz was the major CBz in both the gaseous and solid phase. More PCDD/Fs were found in the solid phase with the decrease of temperature, while CBzs exhibited the opposite trend. Furthermore, activated carbon with a low surface area and mesoporous volume showed low flue gas removal efficiencies for PCDD/Fs and CBzs in the flue gas. The fraction of PCDD/Fs in the solid phase largely decreased when the flue gas passed through the fabric filter. Additionally, the memory effects of the aged filters increased the fractions of 234678-HxCDF, 1234678-HpCDF and 1234678-HxCDD. Most important, the relationships between PCDD/Fs and CBzs in the flue gas and fly ash were analyzed, respectively. In the gaseous phase, most of the CBzs displayed high correlation coefficients with PCDD/Fs, especially 123-TrCBz (R2 > 0.8). In the solid phase, low correlation coefficients were found between CBzs and PCDD/Fs except for 135-TrCBz and 123-TrCBz (R2 = 0.8). A remarkable correlation was also found between 124-TrCBz in the flue gas and PCDD/Fs in the fly ash. We conclude that TrCBzs may be regarded as the best indicator for PCDD/Fs in both flue gas and fly ash.