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As indispensable strategic materials for high-tech industries, rare earth elements and yttrium (REY) have become particularly important in recent years, raising the demand of developing new approaches for reclamation of REY from REY-rich materials such as coal combustion products (CCPs). In this study, five coal-fired power plants (CFPPs) in Guizhou of southwest China were selected for investigating REY concentrations of solid samples, atmospheric emissions, and recovery potentials. REY concentrations of feed fuels are higher in this study (147.2-468.6 mg/kg) than what have been reported previously for coals in China and the world. REY atmospheric emissions are extremely low (38.70-180.11 mg REY/t coal). REY are enriched in bottom ash and fly ash, with average of 658 ± 296 mg/kg and maximum of 1257 mg/kg from the five CFPPs. Relative enrichment factors (REF) of REY in bottom ash and fly ash compared with the feed fuel are 0.86-1.02 and 0.91-1.04, respectively. REY concentrations in desul-furized gypsum are very low (6-17 mg/kg), and that is mostly inherited from limestone. Critical REY (Nd, Eu, Tb, Dy, Y, and Er) in bottom/fly ash account for 34％-39％of the total REY and the outlook coefficients (Coutl) are in the range of 0.89-1.11. This study indicates a promising prospect to reclaim REY from REY-rich CCPs (bottom and fly ash) in CFPPs in Guizhou, especially in the central-north Guizhou, although such practices require further technology advancement.