Thallium (Tl) is a highly toxic trace metal posing a significant threat to human health. Tl pollution in soils and chronic Tl poisoning related to Tl-rich sulfides weathering in the Lanmuchang mine of southwest Guizhou province, China, have been intensively studied in recent years. And yet, there are few studies on the role of secondary sulfate minerals associated with Tl mobility in this area. The sulfate minerals were characterized by XRD and SEM-EDS. The concentrations of Tl and other elements were determined by ICP-MS. The results show that sulfate minerals are predominantly melanterite, halotrichite, and fibroferrite. The average contents of Tl in rock, sulfate minerals, and soil samples were 156.4, 0.11, and 72.1 µg g⁻¹, respectively. This study suggests that Tl in the mineralized rocks entered soils by pyrite oxidation with less scavenged of the sulfate minerals. The dissolution of the ferric sulfate minerals accelerates pyrite oxidation and maintains soil acidity, and this likely enhances Tl mobility from soil to crops.