Degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in municipal solid waste incinerator fly ash is beneficial to its risk control. Fly ash was treated in a full-scale thermal degradation system (capacity 1 t d^–1) to remove polychlorinated dibenzo-p-dioxins and dibenzofurans. Apart from the confirmation of the polychlorinated dibenzo-p-dioxin and dibenzofuran decomposition efficiency, we focused on two major issues that are the major obstacles for commercialising this decomposition technology in China, desorption and regeneration of dioxins and control of secondary air pollution. The toxic equivalent quantity values of polychlorinated dibenzo-p-dioxins and dibenzofurans decreased to <6 ng kg^–1 and the detoxification rate was >=97% after treatment for 1 h at 400 °C under oxygen-deficient conditions. About 8.49% of the polychlorinated dibenzo-p-dioxins and dibenzofurans in toxic equivalent quantity (TEQ) of the original fly ash were desorbed or regenerated. The extreme high polychlorinated dibenzo-p-dioxin and dibenzofuran levels and dibenzo-p-dioxin and dibenzofuran congener profiles in the dust of the flue gas showed that desorption was the main reason, rather than de novo synthesis of polychlorinated dibenzo-p-dioxins and dibenzofurans in the exhaust pipe. Degradation furnace flue gas was introduced to the municipal solid waste incinerator economiser, and then co-processed in the air pollution control system. The degradation furnace released relatively large amounts of cadmium, lead and polychlorinated dibenzo-p-dioxins and dibenzofurans compared with the municipal solid waste incinerator, but the amounts emitted to the atmosphere did not exceed the Chinese national emission limits. Thermal degradation can therefore be used as a polychlorinated dibenzo-p-dioxin and dibenzofuran abatement method for municipal solid waste incinerator source in China.