This review covers characteristics and potential applications of various versions of the X-ray fluorescence (XRF) spectrometry for analyzing both liquid and solid samples. Particular emphasis is given to research published within the past decade, as information on XRF’s previous applications can be found in earlier reviews and monographs. The results of experiments on determining fundamental atomic parameters, such as mass absorption coefficients, fluorescence yields, transition probabilities for the emission of specific lines of elements, and nonradiative transition probabilities. Additionally, the review addresses the capabilities of newly designed models of XRF spectrometers developed in recent years. The application of total reflection X-ray fluorescence spectrometry for diverse samples is examined in greater detail. Furthermore, the document presents data on the utilization of XRF in investigating nanoparticles of some typical materials. These particles exhibit qualitatively novel properties and have become a focal point of nanotechnology, an area rapidly developing in the last few decades.