This article describes the recent research progress in the field of crystalline metal‐chalcogenide superlattices containing tetrahedron‐shaped nanoclusters as building units. With the development of new synthetic strategies and structural concepts, new clusters that are members of three series of tetrahedral clusters (i.e., supertetrahedral clusters, pentasupertetrahedral clusters, and capped supertetrahedral clusters) have been prepared and organized into extended frameworks with a variety of topologies, such as single diamond, double diamond, ABW, CrB
4
, SOD, cubic C
3
N
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, UCR‐1, ICF‐24, ICF‐25, α‐ and β‐quartz, moganite, and boracite. These materials show rich compositional diversities with tunable optical properties, microporosity, and ion‐exchange properties, suggesting their potential applications in photocatalysis, fast‐ion conductors, solar cells, etc.