In the face of a challenging situation for yearly e-waste (EW) increment and disposition, EW co-incineration (EWC) with municipal solid waste (MSW) is a promising solution whose emission characteristics remain unclear. This study is conducted in a 400 tons/day MSW incineration (MSWI) plant to characterize polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and fly ash (FA) properties. Analytical methods include high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) for PCDD/ F determination, as well as X-ray diffraction (XRD), X-ray fluorescence (XRF), ion chromatography (IC), and leaching toxicity test for FA. The results indicate that toxic PCDD/F amounts are doubled by EWC in both primary exhaust gas (EG) and FA with international toxic equivalent quantity (I-TEQ) concentrations of 19.00 ± 6.32 ng I-TEQ/Nm 3 and 1.33 ± 0.56 ng I-TEQ/g. After the clean-up of the air pollution control system (APCS), emitted PCDD/Fs in solid and gas phases, as well as major air pollutants (CO, NO x , SO 2 , HCl, and particulate matter), are permissive within the limit values of national standards GB 18485-2014 and GB 16889-2008. Distribution patterns for 136 PCDD/F isomers are analogous in both MSWI and EWC conditions. De novo synthesis is always the major formation route for both EWC and MSWI conditions, while dibenzodioxin/dibenzofuran (DD/ DF) chlorination also contributes. The generation of 136 PCDD/Fs is enhanced by EWC, and the correlation coefficients of Cl and Cu in the fuel with the generation of 136 PCDD/F isomers are found to be R = 0.92 and 0.88, respectively. The main components in FA from MSWI and EWC differ less, both containing CaO, SiO 2 , and Al 2 O 3 . However, Cl and Cu contents, as well as leaching toxicity in FA are elevated by EW. Heavy metals, except for Cd, Ni, and Pb, meet the requirement of the standard.