The advancement of co-processing solid wastes in coal-fired boilers is significant for waste recycling and contributes to the sustainable development of the coal-fired power industry. However, concerns over the emission of dioxins during co-processing have prompted a comprehensive investigation into the dioxin emission properties. In this study, the PCDD/F emission concentrations of seven coal-fired boilers, including three pulverized coal boilers and four circulating fluidized bed boilers were examined. The results indicate that co-processing solid wastes in coal-fired boilers did not lead to an increase in the mass concentration of dioxins in either the flue gas or solid samples, and the international toxic equivalents (I-TEQ) of dioxins in the flue gas complied with prevailing emission standards (0.1 ng I-TEQ/Nm3) in China, proving that coal-fired boilers co-processing would not raise the emission risk of dioxins. The types of waste during co-processing had minimal effect on the I-TEQ of dioxins. A significant proportion of PCDD/Fs was observed in the ash samples, while only 13.0–25.7% and 0.7–6.8% of dioxins were distributed in the boiler slag and the flue gas, respectively. The emission factor of dioxins under the blank conditions ranged from 0.009 to 0.327 ng I-TEQ/kg-coal, while it ranged from 0.015 to 0.129 ng I-TEQ/kg-(coal+waste) under the co-processing conditions. The reduction of emission factor under co-processing condition could be attributed to the significant decrease of dioxins I-TEQ.