High⁃nuclearity silver clusters have attracted increasing attention not only owing to their various structures, but also due to their potential applications in many fields. The synthesis of functional high⁃nuclearity silver clusters is still a huge challenge because of the unpredictability of self⁃assembly. In this paper, we reviewed the research progress of the silver clusters constructed from AgC≡CtBu and AgStBu ligands. The synthesis strategies of these silver clusters are introduced. The formation rules of these high⁃nuclearity silver clusters were studied. The purities, morphologies and stabilities of the high⁃nuclearity silver clusters were analyzed, and their potential luminescence and electrochemical properties were researched. The application prospect and developing direction of this kind of silver cluster materials are also forecasted.