High?nuclear silver clusters have recently received increasing attention owing to their interesting electronic structures and diverse geometric structures. According to Lewis acid?base theory and coordination chemistry theory, silver ions, as acidic centers that provide empty orbitals, often combine with organic ligands that carry lone pairs of electrons as basic centers to form stable coordination compounds. Alkynyl, thiol, and organic phosphine ligands have been widely used to coordinate with silver(I) ions to form silver clusters with various structures. This paper introduced the research progress of the silver chalcogenide clusters constructed by tert?butyl mercaptan ligand, as well as the synthesis methods and structures of silver chalcogenide clusters with different configurations, and explored its potential luminescence and electrochemical properties. The application prospects and development directions of silver chalcogenide clusters was prospected.