Abstract: Per- and polyfluoroalkyl substances (PFAS) are a class of persistent organic pollutants that are difficult to degrade, bioaccumulative, and have long-range transport properties. Therefore, China, the United States, and the EU have taken a series of legal measures to regulate PFAS since 2023. Reference materials play an important role in PFAS regulation and should be given sufficient attention. Currently, the PFAS reference material system in China is deficient, because not only pure substances and standard solutions, but also isotopically labeled reference materials and matrix reference materials need to be further enriched and developed. In addition, this paper reviews the application of some PFAS reference materials in environmental analysis over the past five years, providing novel uses of reference materials for environmental analysis and monitoring practitioners. Finally, some suggestions are provided for the construction of the PFAS reference material system in China.