Abstract: X-Ray fluorescence spectroscopy (XRF) has become one of the widely used methods for main and trace elements analysis in geological samples because of its characteristics of non-destructive, fast, environmental friendly and high analytical precision. However, there are still some difficulties in practical analysis of geological samples with XRF due to the complexity and diversity of mineral composition, physical structural characteristics (e.g., size, shape, delamination and inclusions) and chemical composition of geological samples. This paper reviews analysis difficulties in geological samples with XRF from five aspects including small size samples and precious samples analysis, the application of scattering effect, the analysis of volatile elements, variable valence elements and rare metals. It is indicated that the preparation of small beads or pellets which are easy to save and facilitate repeated measurement is a suitable method for small sample size and precious samples. The XRF scattering effect can be used to obtain more chemical information in the samples with unknown composition and to correct the error of analysis in situ of heterogeneous samples. Preparation of ultrafine powder pellet, addition of stabilizer and standard addition method establishing work curve are solutions of volatile element analysis .Relative intensity of characteristic X-ray fluorescence can be used for analysis of valence state and morphology of variable valence elements. Optimization of the calibration curve, preparation of low-dilution (sample to flux ratios) glass beads, excitation at high X-tube voltage and correction of spectral line overlap interference are effective ways for rare metals analysis. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202403150052.