The analysis of rare earth elements had been a hot topic in inorganic analytical chemistry, and it was also a big problem for a long time. In the 1960s and 1970s, the research upsurge in the composition of complex polymetallic rare earth minerals in Bayan Obo and the research upsurge in the geochemistry of trace rare earth elements in the 1970s and 1980s greatly promoted the development of rare earth element analysis technology of geological materials in China. In this paper, the literature of rare earth elements in China and the basic conditions of rare earth element analysis were reviewed from the aspects of Monographs on rare earth element analysis, national standard reference materials for rare earth ores, national standard analysis methods and review papers on rare earth element analysis. In this paper, 63 papers on XRF analysis of rare earth elements in geological materials from 1964 to 2018 in China were collected. The papers were mainly reviewed from three aspects: analysis of rare earth elements in ore minerals, trace rare earth elements in various geological materials and micro area in situ analysis of rare earth elements in ore minerals. In this paper, the historical contribution of XRF to the determination of REE in early rare earth ores and minerals was briefly introduced. Finally, the existing problems of XRF in the analysis of rare earth elements in geological materials are discussed and suggestions for future development were put forward. There were 126 citations in this paper.