Coal fly ash has long been considered a potential resource for recovery of valuable elements, such as rare earth elements (REE), which are retained and concentrated upon combustion of coal feedstocks. Understanding REE occurrence within fly ash is a key to developing possible recovery methods. Recent results using modern analytical approaches shed light on the distribution REE in fly ash and the approaches required for their recovery. Some of the highest REE contents occur in fly ash derived from U.S. Appalachian Basin coals, and among these, coals influenced by input volcanic ash (Fire Clay coal, Kentucky) are especially enriched. Leaching studies of bulk fly ash show that, as a proportion of the total REE present, samples from eastern U.S. coals are generally less readily extractible than fly ash derived from western U.S. coals having lower REE contents. Direct determinations by ion microprobe show that REE in a range of fly ash samples are partitioned into aluminosilicate glasses formed during melting at boiler temperatures. These glasses comprise the largest mass fraction of coal fly ash. REE-enriched domains are present locally in fly ash at the nanometer scale (as shown by TEM), and these REE coexist with the glass phase. To enable systematic study of these REE, Ce has been proposed as a proxy for the trivalent lanthanides, as supported by speciation determinations demonstrating that Ce occurs in the trivalent form in fly ash. Despite a decreasing proportion of coal use for electric power generation in the U.S. and elsewhere, annual fly ash production, combined with coal ash already in storage, make up a large resource for potential recovery of rare earths and associated critical elements. Further developments in extraction technologies are needed to overcome difficulties in REE concentration and purification to produce REE materials of saleable purity derived from coal ash.