The self-assembly of metal chalcogenide tetrahedral clusters can lead to a family of porous semiconducting materials with uniform pore sizes and high surface area. The single-sized tetrahedral clusters act as building blocks to form well-ordered three-dimensional superlattices in the presence of either organic or inorganic species (including optically active metal complexes) as structure directing agents. The structural analysis based on single crystals reveals detailed information that could help for the understanding of the unique optical and photocatalytic properties of the materials. The diversity of superlattices is achieved by modifying the cluster size, the cluster composition, and the inter-cluster linkage mode. The electronic band structures of the materials can be tuned over a wide range by controlling the chemical compositions and sizes of the clusters. Physical properties such as porosity and gas adsorption properties of the materials have been studied and will be presented. These porous semiconducting materials exhibit high surface area and uniform porosity. They can be used as photocatalytic materials for converting water and carbon dioxide into useful chemicals, as well as electrocatalytic materials for oxygen reduction reaction.