Feed coal, fly ash (FA), and bottom ash (BA) were collected from a 300 MW circulating fluidized bed boiler. A mechanical screen classifier was used to separate and obtain particles with different sizes. The distribution of valuable elements, including aluminum (Al), lithium (Li), and gallium (Ga), and rare earth elements (REE) in the samples was investigated. Results indicate that the contents of SiO 2 and Al 2 O 3 in sized ash particles decreased as the particle size decreased; meanwhile, the contents of CaO, SO 3 , and Fe 2 O 3 apparently increased. The sulfur-fixing product anhydrite tended to be distributed in the fine ash particles. The valuable elements were more enriched in FA than in BA. The Li, Ga, and REE were evenly distributed in FA particles with different sizes. Separating ash particles with a superhigh concentration of these rare elements was difficult using the mechanical screen, but a part of the anhydrite or CaO in circulating fluidized bed ash could be removed easily. The Li and REE in the feed coal were highly associated with quartz, kaolinite, and other fractions containing SiO 2 and Al 2 O 3 . No definitive relationship between the Ga concentration and Al 2 O 3 content in the feed coal and ash samples was observed.