Abstract: As one of the major hazards in coal mining, the transition towards green and resource-efficient technologies for the prevention and control of spontaneous combustion has become an urgent priority for the industry. At the same time, the volume of solid waste generated during coal mining operations continues to rise, placing increasing pressure on the environment. The alkaline components, such as CaO and Al₂O₃, found in fly ash and coal gangue—the most commonly used materials for preventing and controlling coal spontaneous combustion—hold potential for the production of green fire-retardant materials. Applying these materials to prevent and control coal spontaneous combustion underground can achieve large-scale disposal of coal-based solid waste alongside the integrated management of disasters. This paper systematically reviews the sources and properties of coal-based solid waste, as well as research progress regarding their application in the prevention and control of coal spontaneous combustion; it focuses on the technical pathways and mechanisms of fire prevention and suppression technologies utilising coal-based solid waste, including grouting and backfilling, CO₂ mineralisation and sequestration, and gel-foam systems; it identifies issues within the current technical framework—such as insufficient stability of coal-based solid waste properties leading to pipe blockages, safety concerns during application, the susceptibility of flame-retardant properties to failure under high-temperature conditions, and the lack of intelligent fire prevention and suppression systems in coal mines—and offers a forward-looking perspective.