Heterothiometallic clusters with many fascinating configurations can be prepared by liquid or solid state reaction methods. Cluster units with reactive binding sites can be organized into ordered zero-, one (1D)-, two (2D)- and three (3D)-dimensional structures in which they can act as either electron donors or electron acceptors. This article surveys the skeletal structures, syntheses and reactions of heterothiometallic polymeric clusters currently available emphasizing the polymeric structural features of compounds based on reactive cluster unit construction.