This research was designed to investigate the formations of hazardous air pollutants in the MSWs pyrolysis-gasification-melting process. In this survey, PCDDs/PCDFs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofuran) were investigated in the two facilities (A and B facilities). In A facility, the PCDDs/DFs concentrations were 0.88, 2.29, 0.16 ng I-TEQ/$m^3$ respectively on the secondary incinerator, boiler and stack. In B facility, the PCDDs/PCDFs concentrations were 0.22, 0.05 ng I-TEQ/$m^3$ respectively on the pyrolysis-gasification-melting furnace and stack. The concentrations of PCDDs/PCDFs increased due to resynthesis during cooling process in the both facilities. High concentrations of PCDDs/PCDFs isomers were founded as 2, 3, 4, 7, 8-PeCDF, 2, 3, 4, 6, 7, 8-HxCDF and 1, 2, 3, 6, 7, 8-HxCDF orderly in A facility, and 2, 3, 4, 7, 8-PeCDF, 1, 2, 3, 7, 8-PeCDD and 2, 3, 4, 6, 7, 8-HxCDF orderly in B facility.