X-ray fluorescence spectroscopy (XRF) has been widely used in the field of geoscience due to its simple preparation, rapid analysis, environmental friendliness, high sensitivity, and non-destructive examination. Nowadays, Earth system science research has gradually become the focus of Earth science, encompassing global climate change, the interaction of the Earth's spheres, and the environmental changes caused by human activities. The boom in these areas raises new demands for elemental analysis, such as the spatial distribution and speciation of elements, real-time geochemical data in the field, accurate and rapid quantification of low atomic number elements, and the optimization of instrument resolution, sensitivity, detection limit, and so on. These demands also promote the emergence and progress of some new XRF techniques and their application in the field of geoscience. Synchrotron-based micro-X-ray fluorescence spectroscopy and X-ray absorption fine -structure spectroscopy permit in situ mapping of interest elements in samples at the sub-micrometer scale, owing to the superiority of the light source. This allows for the spatially resolved determination of element distribution and speciation, as well as the element oxidation state and coordination environment. The μ-XRF of a laboratory light source is time-saving and convenient compared to a synchrotron radiation device. Additionally, the analysis accuracy of low atomic number elements using laboratory μ-XRF has significantly improved through the upgrade of the X-ray optical tube, detector, and focusing optical system. PXRF enables the rapid analysis of field samples due to its miniaturization and simple sample processing. The XRF core scanner enables high-precision, continuous, and rapid scanning of large-batch cores, thereby overcoming the cyclical limitations of laboratory analysis. This paper reviews the application of several XRF techniques in geological and geochemical analysis over recent years, aiming to provide some ideas and inspiration for researchers in XRF studies and geoscience fields.