Y203 is a common starting material for the preparation of various solid-state luminescent materials. Since the luminescent efficiency of these materials may be adversely affected by the presence of ultratrace rareearth impurities, there has existed a pressing need for an analytical technique capable of assessing the purity of Y203. A comparative evaluation of the X-ray excited optical fluorescence spectra of various yttrium-containing compounds has revealed that YP04 and isostructural YV04 are superior hosts for the ultratrace determination of the Ce to Yb series of impurities occurring at the part per giga (1 in 101 23456789) level in highly purified YA.The unique optical fluorescent spectra of rare-earth activated materials has found widespread application in diverse industrial products such as solid state lasers (YAGNd), color television tubes (Y202S-Eu), and image conversion devices (Yi_zYbz02S • Er) (7). The efficiency of these materials, which are often compounds of yttrium, may be dependent on the presence of rare-earth impurities at the part per million levels because they may contribute to energy transfer processes (2-4). As a consequence, there is a pressing need for the preparation of ultra high purity Y2Os specially free from rare-earth impurities and for the development of sensitive analytical techniques to match these developments. The latter requirement has only recently been met by two simple but sensitive analytical techniques that take advantage of spectrometric methods of detection of the optical line fluorescence of rare-earth impurities excited by electrons, i.e., cathodoluminescence (5-7) or by X-rays (8-11), hereafter referred to as X-ray excited optical fluorescence (XEOF).Our own investigations with the XEOF technique have shown that quantitative results at the fractional ppm level or