The occurrence of impurity elements in raw ore obtained from two major barite mining regions in Guizhou Province was investigated using automatic mineral liberation analysis (MLA), X-ray diffraction (XRD) analysis, and X-ray photoelectron spectroscopy (XPS) among other characterization methods. The chemical and mineral compositions as well as the occurrence of impurity elements in the barite samples were analysed and compared. The results showed that the main components of the barite samples obtained from the two mining areas were similar, and the impurity minerals mainly existed in the form of inclusions and intergrowths. However, the type, content, and occurrence of the main impurity elements were quite different, indicating significant differences between the barite samples obtained from the two areas. The impurity elements found in the barite obtained from Zhenning were mainly Si, Al, and Fe. Alternatively, the impurity elements of the barite obtained from Tianzhu were mainly Si, Ca, Mg, Al, Fe, and C. The occurrence forms of impurity elements in two kinds of minerals were studied respectively. A comparison showed that the barite obtained from Tianzhu exhibits various impurities and a more complex intergeneration relationship in minerals than that obtained from Zhenning. These findings provide a theoretical basis for optimizing the barite beneficiation process and strengthening the comprehensive utilization of resources.