A Cu-In-S semiconductor consisting of a single piece of a super-supertetrahedron of infinite order has been synthesized through the self-assembly of the largest known Cu In S T-5 supertetrahedral cluster. One of the most fascinating structural features of this material is its dual hierarchical architecture. Its open-framework architecture can be considered as a "hollowed-out" cubic ZnS-type structure with exactly 64.8% of the total of 1000 atoms in the 5 x 5 x 5 zinc blende supercell removed. The synthetic realization of this material serves to demonstrate a new method for property engineering of semiconducting materials.