Supertetrahedral Tn clusters are exact fragments of a cubic ZnS type lattice. Thus far, Tn clusters up to T4 with 20 metal sites can be synthesized in a discrete molecular form. Yet, synthesis of larger discrete supertetrahedral clusters still remains a great challenge, likely due to the rapidly increasing negative charge on the cluster as the size goes up. By using organic superbases (DBN and DBU) to help stabilize the negative charge, a family of discrete supertetrahedral chalcogenide clusters with sizes spanning from T3 (10 metal sites) to T5 (35 metal sites) have been made. The T5 cluster represents the largest molecular supertetrahedral Tn cluster known to date.