Tetrahedral chalcogenide clusters, with their well-defined molecular structures and interesting properties, are attractive building blocks for hybrid materials, in which porosity may be integrated with electronic or optical properties. Linkage of tetrahedral clusters often occurs through bridging chalcogenolate ligands, and results in extended structures of inorganic connectivity. However, linkage of tetrahedral clusters via organic ligands is also possible and a number of coordination polymers have already been reported. Recent advances on the synthesis and crystal structures of extended hybrid structures based on tetrahedral clusters are described here. © 2010 The Royal Society of Chemistry.