The present invention is generally directed to methods of making ceramics with nanoscale/microscale structure involving self-assembly of precursor materials such as, but not limited to, inorganic-based block co-polymers, inorganic-/organic-based hybrid block co-polymers, and other similar materials, and to the structures made by such methods. Where such precursor materials are themselves novel, the present invention is also generally directed to those materials and their synthesis.