[Re(6)Q(8)L(6)](4-) (Q S, Se, Te) clusters can serve as promising "building blocks'' for the creation of new porous framworks, nanoparticles and mesoporous materials. Since [Re(6)Q(8)L(6)](4-) clusters have multi-anchoring sites for transition metals, metal-organic complexes, polymers, and multidentated metal complexes, they could be assembled to form various inorganic or organic-inorganic hybrid solids with new various spatial and chemical functions. Because of the controllable architectures and multi-anchoring sites of clusters together with their photoluminescence, rhenium cluster complexes are promising potential candidates as catalysts, chemical color sensors, magnetic materials, gas storage materials, optoelectronic, diagnostic agents, and gene/drug carriers. A new type of mesoscale material comprising [Re(6)Q(8)(CN)(6)](4-) and various divalent transition metals in the presence of a liquid crystal template are obtained in 3D cubic, 2D hexagonal, and lamellar phases. The hexahydroxo complexes [Re(6)Q(8)(OH)(6)](4-) (Q S, Se) with high reactivities and a unique rhenium sulfido-cyanide compound, K-8[Re12CS17(CN)(6)] with a C-centered {Re-12} cluster unit were discovered and still many more new rhenium metal cluster complexes at various reaction conditions remain to be explored.