<p>Effective management of hazardous industrial waste is vital for environmental protection and sustainable resource utilization. Spent potlining (SPL), a toxic by-product of aluminum smelting, poses severe ecological risks due to its leachable fluoride and cyanide content, corrosive nature, and potential to emit toxic gases upon contact with moisture. This systematic review comprehensively examines innovative techniques for fluoride detoxification and recovery from SPL, underlining their alignment with circular economy principles. The review evaluates advanced hydrometallurgical and pyrometallurgical approaches, concentrating on their operational efficiency, scalability, environmental performance, and cost-effectiveness. Key fluoride extraction pathways including acid, alkali, and water leaching, as well as calcination, thermal decomposition, and smelting are analyzed to highlight their comparative advantages and limitations. Factors influencing process performance, such as temperature, reagent concentration, and leaching time, are also discussed. Reported studies demonstrate that fluoride recovery efficiencies exceeding 95%, confirming the feasibility of SPL valorization for sustainable waste treatment. Furthermore, the industrial reuse potential of recovered fluoride compounds, such as aluminum fluoride and calcium fluoride, is explored for applications in aluminum electrolysis, ceramics, and metallurgy. Remaining challenges and knowledge gaps are identified, and future research directions are proposed to boost process efficiency, minimize environmental risks, and support large-scale implementation. Overall, this review highlights the significance of innovative SPL recycling technologies in advancing environmentally responsible aluminum production and promoting sustainable resource recovery worldwide.</p>