Abstract: Conditions of fusion of cryolite sample for XRFS analysis were studied,and a mixture of lithium tetraborate (67 g) and lithium metaborate (33 g) was used as flux to avoid loss of fluorine during the fusion process.Mass ratio of flux to sample of 10 to 1.5 was taken in the fusion to give a glassy disc-shaped melt,suitable to be used for XRFS analysis.Matrix effect and interferences due to overlapping of spectral lines of elements were corrected by the theoratical α coefficient and the basic parameters.By the proposed method,3 main components (F,Al and Na),and 5 main impurities (SiO2,Fe2O3,SO3,CaO and P2O5) were determined.In applying the method to the analysis of 4 standard samples or known samples,the results obtained were in consistency with the standard values or known values.