Abstract: X-ray Fluorescence Spectrometry (XRF) was a well proven technology established in the early 1980s, and was the preferred method for major, minor and trace elements analysis in the lab and field and suitable for non-destructive analysis and in situ analysis. In this paper, the development of XRF, Wavelength Dispersion XRF (WDXRF), Energy Dispersion XRF (EDXRF), and X-ray Fluorescence Spectroscopy for on-site and in-situ analysis and their characteristics for the last 30 years are reviewed. The application field and basis on total reflection and polarization properties for XRF, such as polarization EDXRF, microbeam XRF and total reflection XRF are also discussed. The development history of matrix correction and the quantitative analytical application of the basic parametric method of the Sherman equation reviewed. The debates about the physical meaning of the matrix correction in the research community and the limitation of the Sherman equation are discussed in detail. The basic parametric method is discussed as to how to improve the accuracy of results obtained by routine quantitative analysis and semi-quantitative analysis. We conclude with the applications of stoichiometry and data processing in XRF. The algorithm combination of an artificial neural network and a basic parametric method is a new direction to improve the accuracy and stability of the matrix correction.