Abstract: With sampling preparation by glass fusion, an X-ray fluorescence spectrum (XRFS) analysis method is established for multi-element test in barite. Preparing 0.5000 g of sample for test, mixing it with 5.000 g of special flux for XRFS, and melting the mixture in the high-frequency bead maker in 1150℃ for 8 minutes, then cooling the sample to room temperature in dryer, finally weighing the accurate mass of the glass. With computer test, to get the data of the element contents in the glass. The actual element contents of the sample is finally obtained by conversion. The theoretical α-coefficient method and empirical coefficient method are adopted for regression calibration of the absorption enhancement effects between the coexisting elements. The tested relative standard deviation of this method for each element in barite ranges from 0.2% to 4.7%, with a detection limit between 3.3×10^-6 and 170.6×10^-6. A reasonable result is obtained for the tested data compared with the national standard material.