<p>Municipal solid waste incineration fly ash, classified as hazardous waste, poses a significant environmental threat due to its high content of heavy metals and dioxins. This paper provides a comprehensive review on the application of plasma vitrification, an advanced thermal technology, for the detoxification and resourceization of this material. The core mechanisms of plasma vitrification, namely the ultra-high temperature-enabled thermal decomposition of dioxins and the effective encapsulation of heavy metals within a stable, glassy silicate matrix, are critically examined. This paper systematically analyzes various plasma system configurations and their key operational parameters that govern processing efficiency. A major highlight of plasma vitrification is the technology’s consistent performance: achieving near-complete destruction of dioxins and reducing the leaching toxicity of heavy metals to levels well below regulatory thresholds. Finally, by comparing practical application cases, the advantages of plasma vitrification technology in volume reduction, processing efficiency, and environmental safety were highlighted. The conclusion draws that plasma vitrification serves as an efficient and sustainable solution for hazardous fly ash management.</p>