Inorganic polymers are relatively unexplored because the efficient formation of macromolecular chains from atoms of transition metals and main group elements has presented a synthetic challenge. Nevertheless, these materials offer exciting opportunities for accessing properties that are significantly different from and which therefore complement those available with the well-established organic systems. Inorganic block copolymers are of particular interest for the generation of functional, nanoscale supramolecular architectures and hierarchical assemblies using self-assembly processes. This article focuses on research in my group over the past decade, which has targeted the development of new and controlled routes to inorganic polymers and their subsequent use in forming supramolecular materials as well as studies of their properties and applications. The use of ring-opening polymerization (ROP) and transition-metal-catalyzed polycondensation approaches are illustrated. Controlled ROP procedures have been developed that allow access to polyferrocene block copolymers that self-assemble into interesting nanoscopic architectures such as cylinders and superstructures such as flowers. The future prospects for inorganic polymer science are discussed, and a growing emphasis on the study of supramolecular inorganic polymeric materials is predicted.