Abstract: A series of mixtures of the CRM or standard sample of alumina and dolomite, primary standard of aluminum oxide and extrapurity potassium chloride and sodium chloride, with their exact masses obtained by applying the Excel formula algorithm, was prepared, and fused with anhydrous lithium tetraborate in a Pt-Au crucible. The 12 pieces of glassy melts obtained formed a series of standard samples having the contents (w%) of their components (i.e., SiO2, Al2O3, MgO, Na2O, K2O, Fe2O3, CaO and TiO2) distributed in gradients, and were used as standard in XRFS analysis of corundum refractories, under prescribed parameters of analytical channels for the 8 components. Substantial corundum refractory samples were analyzed by the proposed method using the selfprepared standard samples, with results in consistency with those found by chemical methods and values of RSD′s (n=10) less than 12%. A separate portion of the primary standard Al2O3 was taken and analyzed in the same way as a blank test to compensate for the interferences of trace elements in the matrix.