A method of making nanoscale ordered composites of covalent ceramics through block copolymer-assisted assembly. At least one polymeric precursor is mixed with a block copolymer, and self-assembly of the mixture proceeds through an annealing process. During the annealing step, the polymeric precursor cross-links to form a structure robust enough to survive both the order-disorder transition temperature the block copolymer and the pyrolysis process, yielding ordered nanocomposites of high temperature ceramic materials. The method yields a variety of structures and morphologies. A ceramic material having at least one ceramic phase that has an ordered structure on a nanoscale and thermally stable up to a temperature of at least about 800.degree. C. is also disclosed. The ceramic material is suitable for use in hot gas path assemblies, such as turbine assemblies, boilers, combustors, and the like.