<p>The demand for novel, environment-friendly, and mostly cost-optimized rare earth elements (REEs) extractions is essential for their vital roles in defense sectors, clean energy, consumer products, and different security applications. Primary sources of REEs are limited and coupled with various processing problems. Among several REEs, cerium and yttrium are of significant industrial importance. Cerium dioxide (CeO₂) is widely utilized as a catalyst and oxygen storage material in automotive exhaust systems, fuel cells, and environmental remediation processes, owing to its remarkable redox behaviour and high oxygen mobility. It also serves as an efficient glass-polishing agent and UV-protective additive in optical coatings. Yttrium oxide (Y₂O₃), on the other hand, is an essential component in high-temperature ceramics, phosphors, and thermal barrier coatings because of its superior thermal stability, corrosion resistance, and optical transparency. Additionally, Y₂O₃ is used as a stabilizer in zirconia ceramics and as a host material for luminescent and laser applications. The unique physicochemical characteristics of CeO₂ and Y₂O₃ make them indispensable in energy, environmental, and advanced material applications, highlighting their importance in sustainable technological development. A list of the most recent articles being reviewed for yttrium and cerium extraction from coal fly ash (CFA). The process routes are very extensive and lengthy, and limited to laboratory scale only. Firstly, this review article briefly describes existing major extraction methods for REEs. Thereafter, a novel extraction approach from CFA via the acid-based route with a customized Centrifuge filter separation technique is proposed. This will bridge the gap between laboratory-scale and industrial scale.</p>