In order to understand the effect of different amounts of powder-activated carbon (PAC) injection and bio-solution (NOE-7F) addition on the removal efficiencies of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant with Waelz rotary kiln process, the PCDD/F concentrations in the stack flue gasses were measured and discussed. In the amount of 20, 40 and 50 kg/h PAC injection, the removal efficiencies of PCDD/Fs in the stack flue gas were 86, 96 and 97%, respectively. While adding more amounts of PAC did enhance the removal efficiencies, the reduction fractions of low chlorinated PCDD/F congeners were much higher than those of highly chlorinated PCDD/F congeners. Particularly, a lower amount of PAC injection (20 kg/h), not only cannot remove highly chlorinated PCDD/Fs, but also the carbon surface of the PAC can act as a precursor for the formation promotion of highly chlorinated PCDD/F congeners. The addition of NOE-7F in the raw materials had the dechlorination effect on the PCDD/F removal and mainly inhibited highly chlorinated PCDD/F formation. The combination of both PAC injection and NOE-7F addition has a high potential for practical application.