Based on the testing data by the inductively coupled plasma mass spectrometry (ICP-MS), X-rays diffraction (XRD) and so on, the distribution, occurrence and geological controls of the rare earth elements (REEs) in the high-sulfur coal seam of the Lower Permian Liangshan formation from Kaili, eastern Guizhou was investigated. The results showed that the REEs content in Kaili’s coal seam was evidently higher than the average contents of REEs in Chinese, America as well as the world’s coals, and the light REEs (LREEs) were comparatively rich, which indicated that the source of those in the coal seam were consistent. It was suggested that the some of REEs in the coal seam might occur in the pyrite, and another with primary enrichment might be hosted in the inertinite and exinite. The peat bog with the weaker water dynamics, subalkaline and reduction was in much favor of the REEs enrichment in the coal seam. The effect of the sea water to the peat bog was one of the important causes in the occurrence of the sulfur- and REEs-accumulated environment in the coal.