Volcanic layers in coal seams in southwestern China coalfields have received much attention given their significance in coal geology studies and their potential economic value. In this study, the mineralogical and geochemical compositions of C19 and C25 coal seams were examined, and the following findings were obtained. (1) Clay minerals in sample C19-r are argillized, and sedimentary layering is not observed. The acicular idiomorphic crystals of apatite and the phenocrysts of Ti-augite coexisting with magnetite in roof sample C19-r are common minerals in basaltic rock. The rare earth elements (REE) distribution pattern of C19-r, which is characterized by positive Eu anomalies and M-REE enrichment, is the same as that of high-Ti basalt. The concentrations of Ti, V, Co, Cr, Ni, Cu, Zn, Nb, Ta, Zr, and Hf in C19-r are closer to those of high-Ti basalt. In conclusion, roof sample C19-r consists of tuffaceous clay, probably with a high-Ti mafic magma source. (2) The geochemical characteristics of the C25 coals are same as those reported for coal affected by alkali volcanic ash, enrichment in Nb, Ta, Zr, Hf, and REE, causing the C25 minable coal seams to have higher potential value. Such a vertical study of coals and host rocks could provide more information for coal-forming depositional environment analysis, for identification of volcanic eruption time and magma intrusion, and for facilitating stratigraphic subdivision and correlation.