Abstract: The major and minor components (SiO₂, Al₂O₃, Fe₂O₃, TiO₂, K₂O, Na₂O, CaO, MgO, MnO and P₂O₅) in silicate and bauxite with high content of iron and titanium were determined simultaneously by X-ray fluorescence spectrometry. The sample (0.500 0 g) was mixed well with lithium tetraborate-lithium metaborate (Li₂B₄O₇-LiBO₂, 5.000 0 g, mass ratio of 67:33), then 0.6 mL of 200 g·L^-1 NH₄Br solution as releasing agent and 1.0 mL of 500 g·L^-1 NH₄NO₃ solution as oxidant were added, the mixture was pre-melt for 2 min and melt for 8 min at 1 100℃ to prepare the fuse piece. The calibration curves were plotted by using national level standard substances and artificial calibration samples of soil, stream sediment, rock, bauxite and kaolin ore. The proposed method was applied to the determination of the major and minor components in certified reference materials and real samples of silicate and bauxite, the results were consistent with the certified values and those obtained by chemical method, and RSDs (n=12) were less than 8.0%.