Standard samples ware artificially synthesized, and powder was pressed into the samples. Using the ZSX Primus Ⅱ type X-ray fluorescence spectrometry, direct assayed the quality fraction of rare elements Nb, Ta, Th and Zr in minerals. Spectrum lines overlap interference was corrected by interference elements number. Absorption-enhancement effects, between the elements, were corrected by internal standard and experience coefficient method. Method for the determination of actual samples, the results correspond with chemical method, 10 times the relative standard deviation (RSD) are: Nb₂O₅ 1.19%, Ta₂O₅ 7.31%, ThO₂ 4.23%, ZrO₂ 0.35%.xml:namespace prefix = o ns = "urn:schemas-microsoft-com:office:office" />