The detoxification of municipal solid waste incinerator (MSWI) fly ash dioxins urgently requires an effective treatment technology. In this study, we adopted a single-mode microwave (MW)-based pyrolysis to treat MSWI fly ash under N-2 atmosphere and further elucidated the main influencing factors, including the chemical inhibitor, for dioxin control. The results show that (1) the detoxification process was optimized with a mass ratio of fly ash to SiC of 1:9, 23.1% (wt%) urea addition and pyrolysis temperature of -480 degrees C; (2) the total polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) destruction efficiency and the bioassay-derived 2,3,7,8-TCDD toxic equivalent (Bio-TEQ) removal efficiency reached 98.5% and 97.9%, respectively, accompanied with 1.3% of the total amount of dioxin being submitted to exhaust gas; (3) the MW-based pyrolysis of urea (133-300 C) was favourable for the generation of hot spots as well as the PCDD/F rapid destruction in fly ash. In addition, the leaching toxicity of heavy metals was also partially reduced after MW pyrolysis reactions. To the best of our knowledge, this is the first report adopting a MW-based pyrolysis to eliminate dioxin in MSWI fly ash with the addition of urea, which is a promising alternative to current methods.