In this paper, geochemical characteristics of rare earth elements (REE) in acid mine drainage (AMD) from the Sitai coal mine of Shanxi Province, North China were investigated by determining concentrations of dissolved REEs and major solutes in the AMD samples, concentrations of REEs in the AMD precipitate samples and country rock samples (mudstone and coal), and modeling REEs species in the AMD. The results show that AMD in the Sitai coal mine have high REEs and SO42− concentrations in comparison with several terrestrial waters worldwide. The REE speciation modeling indicates that sulfate complexes (LnSO4+, >60%) and free metal species (Ln3+, 20%–40%) are dominant REEs species in the AMD. AMD of the Sitai coal mine also shows a middle REE-enriched NASC (North American Shale Composite)-normalized pattern. The authors suggest that both REE sulfates (LnSO4+) in the AMD and country rock of coal measures are possible reasons for middle REE-enriched NASC-normalized pattern of the Sitai coal mine AMD. Further work on the AMD precipitates is needed to obtain more information on the origin of the middle REE-enriched NASC-normalized patterns.