Abstract: After ignition at 750-800℃ for 2 h, 0.300 0 g of the sample was mixed well with 4.000 0 g of lithium tetraborate, 3.000 0 g of lithium metaborate, and 0.500 0 g of lithium carbonate in a platinum yellow crucible. Then 0.5 mL of 300 g·L^-1 lithium bromide solution was added into the crucible and the mixture was melted at (1 050±20)℃ to prepare sample sheets. The contents of major and minor components in the high chromium type vanadium slag were determined by X-ray fluorescence spectrometry. Vanadium slag standard samples and a series of calibration samples prepared with the standard samples and the reference substance were used to draw calibration curves to eliminate the matrix effect. The analysis lines were selected and spectral line overlap interference correction was performed. Linear relationships were found between values of the fluorescence intensity and the mass fractions of each component within definite ranges. The method was applied to analysis of high chromium type vanadium slag samples, giving results in consistency with those obtained by titration and inductively coupled plasma atomic emission spectrometry, and RSDs (n=10) were between 0.030% and 7.3%.