Solid state phosphorous is an important phosphorus speciation controlling the phosphorous bioavailability and mobility in the environment. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy, with its unique advantage of being a non-destructive method in identifying the local chemical information of target element at molecular level in situ, has become one of the frontier technologies for characterizing the speciation of chemical substances and clarifying the microscopic mechanisms of chemical reactions, attracting extensive attention in the field of environmental chemistry. This paper briefly introduced the basic theory of phosphorus XANES spectroscopy, summarized the applications of XANES spectroscopy in the researches of solid state phosphorus speciation in minerals, soils, and organic fertilizers, and analyzed the challenges and prospects of the applications of XANES spectroscopy in identifying the solid state phosphorus speciation in the environmental samples. It was pointed out that XANES spectroscopy should combine with other microscopic spectroscopic techniques and macroscopic analytical methods, complementing each other, to provide a comprehensive and effective technical support for the research of the speciation characterization and transformation mechanisms of phosphorus in the environment.