Abstract: A chemical method was used for the preparation and enrichment of four rare earth concentrates (bastnaesit, monazite, xenotime and weathering crust Elution-deposited rare earth ore). Mixed flux, mainly consisting of borate, was applied to eliminate the presence of the structure of minerals with high temperature fusion. Increasing the flux dilution ratio reduces the matrix effects between elements. The calibration curve was established by artificial standard materials and the overlap effect between spectral lines was corrected by mathematical method. Compared with data by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), the contents of rare earth elements and uranium and thorium were determined by X-ray Fluorescence Spectrometry (XRF). The REE-3 sample was measured 12 times and the detection limit was 0.9-42.1 μg/g. The relative standard deviations (RSD) for all components were less than 10%. Applied to national standard reference materials of rare earth elements, all the data by this method were in agreement with those by other analytical methods, within detection limits and precision. All reported data were adopted.