Display omitted •Structural features of silver sulfide/thiolate and silver thiolate clusters.•Structural features of silver selenide/selenolate clusters.•Structural features of silver tellurolate and silver telluride/tellurolate clusters.•Structural features of silver dithiophosphate/diselenophosphate clusters.•Optical and electronic properties of high nuclearity silver(I) chalcogenolate clusters. The high-nuclearity silver(I) clusters, a novel class of supramolecular assembly of silver(I) complexes, were usually prepared by incorporating silver ions with various ligands. Notably, a large number of argentophilic interactions exist in the high-nuclearity silver clusters. These interactions influence significantly a variety of structural and other physical characteristics. Thus, we will summarize the synthesis and structure of high-nuclearity silver(I) clusters with chalcogenide E2− (E=S, Se and Te), chalcogenolate RE− (E=S, Se and Te), dichalcogenophosphate (RO)2PE2− (E=S and Se), and dichalcogenophosphonate R(R’O)PS2− or RP(O)S22−. This results in deeper understanding of the relationship between synthesis conditions and the finally isolated products. The literature survey is up to December 2015 and the review represents the first article covering the span of various types of high-nuclearity Ag-E clusters and should contribute considerable value for future research.