The effects of thermal treatment temperature and CaO addition on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) content in the fly ashes from a medical waste incinerator with high chlorine content (7.5%) were investigated. Two kinds of batch mode were examined: without CaO addition under the temperature range of 50-850°C, and with CaO addition at various Ca/Cl molar ratios (CCR = 0.8-44.3) at 250°C.The results show that the PCDD/F content in raw fly ash was 6.20 ng I-TEQ/g. When elevating the temperature from 50 to 400°Cwithout CaO addition, the PCDD/F content dramatically increased from 5.38 to 575 ng I-TEQ/g. Even at 850°C, the PCDD/Fs were not destructed apparently and were still with a concentration of 401 ng I-TEQ/g. However, with the addition of CaO at CCR = 17.7 at only 250°C, the removal ratio of PCDD/Fs reached to 87.2% and the PCDD/F content was significantly reduced to 0.889 ng I-TEQ/g, which meets the soil pollution standard of Taiwan EPA (1 ng I-TEQ/g) and could be considered as backfill. CaO addition was proven efficiently to enhance the reduction rate of PCDD/Fs in fly ashes during the thermal treatment at a low temperature, as well as inhibit the formation of PCDD/Fs.