The lowermost Late Permian coal seam (C4 Coal) in the Tongzi Coalfield offers an opportunity to investigate the influence of terrigenous detrital materials from the Qianbei Upland on the mineralogical and geochemical patterns of the C4 Coal. The minerals are mainly dominated by pyrite and, to a lesser extent, tobelite, kaolinite, and calcite, along with traces of Al-oxyhydroxide minerals. The various degrees of marine influence may have resulted in the variation in the amount of Fe-sulfides (e.g., pyrite) and elements having Fe-sulfides affinity. Furthermore, the abundant Fe ions involved in the formation of Fe-sulfides were most likely derived from the claystone on the Qianbei Upland. The tobelite identified in the C4 Coal probably originated from the interaction between pre-existing kaolinite and NH4+ from NH3 released from the thermally affected organic matter at least shortly after the highly volatile bituminous stage under NH4+-rich and K+-poor conditions. The terrigenous detrital materials were derived from two possible sediment-region sources—the Qianbei Upland and Kangdian Upland—which is different from Late Permian coals in Western Guizhou Province. The claystone on the Qianbei Upland may have served as parent rock, as indicated by the presence of the Al-oxyhydroxide minerals as well as low SiO2/Al2O3 ratio (0.66 on average) and low quartz content. Meanwhile, the detrital materials from the Kangdian Upland most likely originated from the erosion of the felsic rocks at the uppermost part of the Kangdian Upland, as evidenced by the high Al2O3/TiO2 ratio (36.0 on average) and the strongly negative Eu anomaly (0.61 on average).