An entirely new type of chalcogenide cluster and a new structural mechanism for the formation of large semiconducting tetrahedral clusters have been revealed as a result of crystallization of a templated indium sulfide consisting of an unprecedented cluster, In(38)S(65), which is the largest supertetrahedral cluster based on trivalent metal ions. At the core of this cluster is In(10)S(13), which can be considered as a fragment of the NaCl-type lattice. The In(10)S(13) cluster is coupled to four In(4)S(10) supertetrahedral T2 clusters and four In(3)S(3) hexagonal rings to give In(38)S(65), which is also the largest inorganic chalcogenide supertetrahedral cluster, superseding a supertetrahedral T5 cluster with only 35 metal sites.