The demand for rare-earth elements is expected to grow due to their use in critical technologies, including those used for clean energy generation. There is growing interest in developing unconventional rare-earth element resources, such as coal and coal byproducts, to help secure domestic supplies of these elements. Within the U.S., Appalachian Basin coals are particularly enriched in rare-earth elements, but recovery of the elements is often impeded by a resistant aluminosilicate matrix. This study explores the use of calcination and sodium carbonate roasting pre-treatments combined with dilute acid leaching to recover rare-earth elements from Appalachian Basin coals and underclay. The results suggest that rare-earth element recovery after calcination is dependent on the original mineralogy of samples and that light rare-earth minerals may be more easily decomposed than heavy rare-earth minerals. Sodium carbonate roasting can enhance the recovery of both light and heavy rare-earth elements. Maximum recovery in this study, ranging from 70% to 84% of total rare-earth elements, was achieved using a combination of calcination and sodium carbonate roasting, followed by 0.25 M citric acid leaching.