Abstract: Traditionally, the percentage sum method is used to check the data quality of total analysis of constituents for silicate rock. For samples with a high content of trace elements, the contents of major elements obtained by X-ray Fluorescence Spectrometry (XRF) will deviate from the true values, regardless of trace elements, as will its corresponding matrix effect to the major element. The method described in this paper improves the accuracy of major element content in silicate samples with a high content of Sr and Ba， through extending the calibration curve′s quantitative range of Sr and Ba by Chinese National Standard Materials and artificial standard materials, and applying a matrix correction coefficient of Sr and Ba to the major element calibration procedure. The validity of the method was substantiated by analyzing the national standard materials; the relative standard deviations (RSD) of major elements were less than 2%. Additionally, analysis results of major elements of national standard materials and artificial standard materials, which do not participate in regression were basically in accordance with reference contents. The method can be used to satisfy the analysis of silicate rock and the sum results of all major elements meet the standard of specification of testing quality management for geological laboratories (99.3% to 100.7%).