In this paper, a bench-scale simulated cement kiln was used to study the emission characteristics, as well as the main factors that influence them, of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), heavy metals, and hydrogen chloride (HCl) in flue gas generated by co-processing combustible components of aged refuse (CCAR). The main combustible components were plastics, textiles, and woods, and the calorific value of CCAR (> 2.5 × 107 J kg–1) was much higher than that of original municipal solid waste (OMSW). De novo synthesis was the dominant PCDD/F formation pathway during the co-processing of CCAR, and CCAR with higher chlorine and Cu content tended to generate more PCDD/Fs. The concentration of the PCDD/Fs produced by the pure raw meal used in this experiment was 3.25 ng m–3 (0.33 ng I-TEQ m–3), which increased to 3.87 (0.56), 6.27 (0.69), or 5.77 ng m–3 (0.72 ng I-TEQ m–3) when CCAR from different landfill periods was mixed in, with the more chlorinated substituted PCDD/F congeners, especially 1,2,3,4,6,7,8-HpCDF, exhibiting relatively high concentrations. However, the less chlorinated substituted PCDD/Fs, especially 2,3,7,8-PCDD and 2,3,4,7,8-PeCDF, contributed the major share of the I-TEQ value. Feeding CCAR through the raw meal inlet increased the formation of PCDD/Fs. Principal component analysis (PCA) was conducted to identify the similarities and differences between congener distributions among the various samples. Overall, the co-processing of CCAR increases the concentration of pollutants and requires more effective technologies for controlling emissions.