Precious metal nanoclusters have unique electronic structure and fluorescent properties, and can be used as fluorescent probes in a wide range of applications such as biomarkers and ion detection. This paper reviews the preparation methods of thiol-protected silver clusters, including bottom-up and top-down methods, focusing on optimizing the reduction process of the reaction, selecting excellent thiol ligands, changing the pH values of the system, and strictly controlling. The research status of the preparation of thiol-protected silver clusters was introduced in terms of etching time and reaction temperature during the reaction, and ideas and suggestions for further research were provided. At the same time, based on the excellent fluorescence properties of thiol-protected silver clusters, the research progress in the detection of small molecules such as Cu2+, Hg2+, I- and cysteine was introduced. Finally, it was pointed out that the fluorescence quantum yield and safety of metal nanoclusters are improved, and the reaction mechanism of metal nanoclusters with heavy metal ions and biomacromolecules is studied in depth, and the synthesis methods of high purity and diversity alloy clusters or transition metal nanoclusters are explored. The preparation of fluorescent sensing materials for the realization of highly efficient thiol-protected silver clusters is a hot trend in future research.